Method of synthesizing molecular sieves

ABSTRACT

The invention is directed to a method of synthesizing a molecular sieve. In particular, the invention is directed to a method for synthesizing a molecular sieve, especially a silicoaluminophosphate molecular sieve, in the presence of a templating agent and a polymeric base. The invention is also directed to formulating the molecular sieve into a catalyst useful in a process for producing olefin(s), preferably ethylene and/or propylene, from a feedstock, preferably an oxygenate containing feedstock.

RELATED APPLICATION DATA

None

1. Field of the Invention

The present invention relates to a method of synthesizing a molecularsieve. In particular, the invention is directed to a method forsynthesizing a molecular sieve, especially a silicoaluminophosphatemolecular sieve, and to its formulation into a catalyst compositionuseful in a process for producing olefin(s), preferably ethylene and/orpropylene, from a feedstock, preferably an oxygenate containingfeedstock.

2. Background of the Invention

Olefins are traditionally produced from petroleum feedstock by catalyticor steam cracking processes. These cracking processes, especially steamcracking, produce light olefin(s) such as ethylene and/or propylene froma variety of hydrocarbon feedstock. Ethylene and propylene are importantcommodity petrochemicals useful in a variety of processes for makingplastics and other chemical compounds. Ethylene is used to make variouspolyethylene plastics, and in making other chemicals such as vinylchloride, ethylene oxide, ethylbenzene and alcohol. Propylene is used tomake various polypropylene plastics, and in making other chemicals suchas acrylonitrile and propylene oxide.

The petrochemical industry has known for some time that oxygenates,especially alcohols, are convertible into light olefin(s). There arenumerous technologies available for producing oxygenates includingfermentation or reaction of synthesis gas derived from natural gas,petroleum liquids, carbonaceous materials including coal, recycledplastics, municipal waste or any other organic material. Generally, theproduction of synthesis gas involves a combustion reaction of naturalgas, mostly methane, and an oxygen source into hydrogen, carbon monoxideand/or carbon dioxide. Syngas production processes are well known, andinclude conventional steam reforming, autothermal reforming, or acombination thereof.

Methanol, the preferred alcohol for light olefin production, istypically synthesized from the catalytic reaction of hydrogen, carbonmonoxide and/or carbon dioxide in a methanol reactor in the presence ofa heterogeneous catalyst. For example, in one synthesis process methanolis produced using a copper/zinc oxide catalyst in a water-cooled tubularmethanol reactor. The preferred methanol conversion process is generallyreferred to as a methanol-to-olefin(s) process, where methanol isconverted to primarily ethylene and/or propylene in the presence of amolecular sieve.

Molecular sieves are porous solids having pores of different sizes suchas zeolites or zeolite-type molecular sieves, carbons and oxides. Thereare amorphous and crystalline molecular sieves. Molecular sieves includenatural, mineral molecular sieves, or chemically formed, syntheticmolecular sieves that are typically crystalline materials containingsilica, and optionally alumina. The most commercially useful molecularsieves for the petroleum and petrochemical industries are known aszeolites. A zeolite is an aluminosilicate having an open frameworkstructure that usually carries negative charges. This negative chargewithin portions of the framework is a result of an Al³⁺ replacing aSi⁴⁺. Cations counter-balance these negative charges preserving theelectroneutrality of the framework, and these cations are exchangeablewith other cations and/or protons. Synthetic molecular sieves,particularly zeolites, are typically synthesized by mixing sources ofalumina and silica in a strongly basic aqueous media, often in thepresence of a structure directing agent or templating agent. Thestructure of the molecular sieve formed is determined in part bysolubility of the various sources, silica-to-alumina ratio, nature ofthe cation, synthesis temperature, order of addition, type of templatingagent, and the like.

A zeolite is typically formed from comer sharing the oxygen atoms of[SiO₄] and [AlO₄] tetrahedra or octahedra. Zeolites in general have aone-, two- or three- dimensional crystalline pore structure havinguniformly sized pores of molecular dimensions that selectively adsorbmolecules that can enter the pores, and exclude those molecules that aretoo large. The pore size, pore shape, interstitial spacing or channels,composition, crystal morphology and structure are a few characteristicsof molecular sieves that determine their use in various hydrocarbonadsorption and conversion processes.

There are many different types of zeolites well known to convert afeedstock, especially oxygenate containing feedstock, into one or moreolefin(s). For example, U.S. Pat. No. 5,367,100 describes the use of awell known zeolite, ZSM-5, to convert methanol into olefin(s); U.S. Pat.No. 4,062,905 discusses the conversion of methanol and other oxygenatesto ethylene and propylene using crystalline aluminosilicate zeolites,for example Zeolite T, ZK5, erionite and chabazite; and U.S. Pat. No.4,079,095 describes the use of ZSM-34 to convert methanol to hydrocarbonproducts such as ethylene and propylene.

Crystalline aluminophosphates, ALPO₄, formed from corner sharing [AlO₂]and [PO₂] tetrahedra linked by shared oxygen atoms are described in U.S.Pat. No. 4,310,440 to produce light olefin(s) from an alcohol. Metalcontaining aluminophosphate molecular sieves, MeAPO's and ElAPO's, havebeen also described to convert alcohols into olefin(s). MeAPO's have a[MeO₂], [AlO₂] and [PO₂] tetrahedra microporous structure, where Me is ametal source having one or more of the divalent elements Co, Fe, Mg, Mnand Zn, and trivalent Fe from the Periodic Table of Elements. ElAPO'shave an [ElO₂], [AlO₂] and [PO₂] tetrahedra microporous structure, whereEl is a metal source having one or more of the elements As, B, Be, Ga,Ge, Li, Ti and Zr. MeAPO's and ElAPO's are typically synthesized by thehydrothermal crystallization of a reaction mixture of a metal source, analuminum source, a phosphorous source and a templating agent. Thepreparation of MeAPO's and ElAPO's are found in U.S. Pat. Nos.4,310,440, 4,500,651, 4,554,143, 4,567,029, 4,752,651, 4,853,197,4,873,390 and 5,191,141.

One of the most useful molecular sieves for converting methanol toolefin(s) are those ELAPO's or MeAPO's where the metal source issilicon, often a fumed, colloidal or precipitated silica. Thesemolecular sieves are known as silicoaluminophosphate molecular sieves.Silicoaluminophosphate (SAPO) molecular sieves contain athree-dimensional microporous crystalline framework structure of [SiO₂],[AlO₂] and [PO₂] comer sharing tetrahedral units. SAPO synthesis isdescribed in U.S. Pat. No. 4,440,871, which is herein fully incorporatedby reference. SAPO is generally synthesized by the hydrothermalcrystallization of a reaction mixture of silicon-, aluminum- andphosphorus-sources and at least one templating agent. Synthesis of aSAPO molecular sieve, its formulation into a SAPO catalyst, and its usein converting a hydrocarbon feedstock into olefin(s), particularly wherethe feedstock is methanol, is shown in U.S. Pat. Nos. 4,499,327,4,677,242, 4,677,243, 4,873,390, 5,095,163, 5,714,662 and 6,166,282, allof which are herein fully incorporated by reference.

Templating agents are used in the synthesis of molecular sieves,particularly SAPO molecular sieves, as a crystal structure-directingagent or affecting agent. Furthermore, templating agents are typicallynitrogen containing organic bases such as quaternary ammonium salts orhydroxides. Typically, because templating agents are also used tocontrol the pH during the synthesis of molecular sieves, the quaternaryammonium hydroxide is often used instead of the less expensivequaternary ammonium salt. Additionally, the quantity of the templatingagent used is often dictated by the pH of the reaction mixture in whichthe molecular sieve forms. Templating agents are typically used inexcess, relative to its incorporation in the crystalline molecular sieveproduct, in order to control the pH and/or alkaline content in thesynthesis of molecular sieves, for example as described in U.S. Pat. No.4,440,871.

The templating agent is oftentimes the most costly ingredient used insynthesizing molecular sieves. Using a second, less expensive base as apH controller, in addition to a templating agent, in principle leads toa reduction in the cost of synthesizing a particular molecular sieve,provided that the pH controller does not interfere with the synthesis ofthe desired molecular sieve. As described in U.S. Pat. No. 4,440,871 ina SAPO molecular sieve synthesis, using an inorganic base to reduce theamount of organic templating agent, often results in the formation ofundesirable dense phase products. Some organic bases, for instance,dipropylamine, have been combined with a templating agent,tetraethylammonium hydroxide, for the synthesis of a SAPO molecularsieve. Monomeric organic bases such as dipropylamine are volatile andraise various environmental and safety concerns. Additionally, higherpressure equipment is needed for the hydrothermal synthesis of molecularsieves using volatile monomeric organic bases.

Therefore, it would be desirable to have an improved method for reducingthe amount of templating agent utilized in synthesizing a molecularsieve.

SUMMARY OF THE INVENTION

This invention provides a method of synthesizing a molecular sieve, toits formulation into a molecular sieve catalyst composition, and to ituse in a process, preferably a conversion process, for making one ormore olefin(s), particularly light olefin(s).

In one embodiment the invention is directed to a method for synthesizinga molecular sieve utilizing a templating agent, preferably an organictemplating agent, and a polymeric base. In preferred embodiments, thepolymeric base is a polymeric base, or a soluble and/or non-volatilepolymeric base or a non-ionic polymeric base, or a combination thereof,and most preferably the polymeric base is a polymeric imine, preferablya polyethylene imine or polyethylenimine.

In another embodiment the invention relates to a method for synthesizinga molecular sieve, the method comprising the steps of: (a) forming areaction mixture of at least one templating agent and at least one ofthe group consisting of a silicon source, a phosphorous source and analuminum source; (b) introducing to the reaction mixture a non-ionicpolymeric base or a soluble polymeric base; and (c) removing themolecular sieve from the reaction mixture. In one preferred embodiment,the polymeric base is non-volatile and/or has a pH of from about 8 toabout 14 in an aqueous solution, and/or has an average molecular weightM_(W) greater than 500. In another preferred embodiment of thisembodiment, the polymeric base is a polymeric imine.

In the most preferred embodiment the invention relates to a method ofsynthesizing a molecular sieve, the method comprising the steps of: (a)combining a silicon source, an aluminum source, and/or a phosphoroussource; (b) introducing an organic templating agent; (c) introducing apolymeric base; and (d) removing the molecular sieve. In a preferredembodiment, the mole ratio of the organic templating agent to themonomeric unit of the polymeric base is from about 0.01 to 1, preferablyfrom 0.1 to 0.75, and more preferably 0.25 to 0.5.

In another embodiment of the invention the molecular sieve describedabove is formulated into a molecular sieve catalyst composition. In thisembodiment, the molecular sieve removed from step (c) above and step (d)immediately above is combined with a matrix material and optionally abinder to form the molecular sieve catalyst composition of theinvention.

In yet another embodiment, the invention is directed to a process forproducing olefin(s) in the presence of any of the above molecular sievesand catalyst compositions thereof. In particular, the process involvesproducing olefin(s) in a process for converting a feedstock, preferablya feedstock containing an oxygenate, more preferably a feedstockcontaining an alcohol, and most preferably a feedstock containingmethanol.

DETAILED DESCRIPTION OF THE INVENTION Introduction

The invention is directed toward a method for synthesizing a molecularsieve using a templating agent and a polymeric base. It has been foundthat a polymeric base is useful in combination with a decreased amountof templating agent to produce a given molecular sieve. Also, it hasbeen found that the use of a salt as a templating agent, such as aquaternary ammonium salt, rather than the more expensive quaternaryammonium hydroxide, is useful in combination with a polymeric base tosynthesize a molecular sieve. Without being bound to any particulartheory, it is believed that the soluble or neutral polymeric base,especially a polymeric imine, more specifically a polyethylenimine, isuseful to control pH, and therefore, less amount of a basic organictemplating agent, or even a non-basic organic templating agent can beused to synthesize a particular molecular sieve.

Molecular Sieves and Catalysts Thereof

Molecular sieves have various chemical and physical, framework,characteristics. Molecular sieves have been well classified by theStructure Commission of the International Zeolite Association accordingto the rules of the IUPAC Commission on Zeolite Nomenclature. Aframework-type describes the connectivity, topology, of thetetrahedrally coordinated atoms constituting the framework, and makingan abstraction of the specific properties for those materials.Framework-type zeolite and zeolite-type molecular sieves for which astructure has been established, are assigned a three letter code and aredescribed in the Atlas of Zeolite Framework Types, 5th edition,Elsevier, London, England (2001), which is herein fully incorporated byreference.

Non-limiting examples of these molecular sieves are the small poremolecular sieves, AEI, AFT, APC, ATN, ATT, ATV, AWW, BIK, CAS, CHA, CHI,DAC, DDR, EDI, ERI, GOO, KFI, LEV, LOV, LTA, MON, PAU, PHI, RHO, ROG,THO, and substituted forms thereof, the medium pore molecular sieves,AFO, AEL, EUO, HEU, FER, MEL, MFI, MTW, MTT, TON, and substituted formsthereof; and the large pore molecular sieves, EMT, FAU, and substitutedforms thereof. Other molecular sieves include ANA, BEA, CFI, CLO, DON,GIS, LTL, MER, MOR, MWW and SOD. Non-limiting examples of the preferredmolecular sieves, particularly for converting an oxygenate containingfeedstock into olefin(s), include AEL, AFY, BEA, CHA, EDI, FAU, FER,GIS, LTA, LTL, MER, MFI, MOR, MTT, MWW, TAM and TON. In one preferredembodiment, the molecular sieve of the invention has an AEI topology ora CHA topology, or a combination thereof, most preferably a CHAtopology.

Molecular sieve materials all have 3-dimensional, four-connectedframework structure of corner-sharing TO₄ tetrahedra, where T is anytetrahedrally coordinated cation. These molecular sieves are typicallydescribed in terms of the size of the ring that defines a pore, wherethe size is based on the number of T atoms in the ring. Otherframework-type characteristics include the arrangement of rings thatform a cage, and when present, the dimension of channels, and the spacesbetween the cages. See van Bekkum, et al., Introduction to ZeoliteScience and Practice, Second Completely Revised and Expanded Edition,Volume 137, pages 1-67, Elsevier Science, B. V., Amsterdam, Netherlands(2001).

The small, medium and large pore molecular sieves have from a 4-ring toa 12-ring or greater framework-type. In a preferred embodiment, thezeolitic molecular sieves have 8-, 10- or 12-ring structures or largerand an average pore size in the range of from about 3 Å to 15 Å. In themost preferred embodiment, the molecular sieves of the invention,preferably silicoaluminophosphate molecular sieves have 8-rings and anaverage pore size less than about 5 Å, preferably in the range of from 3Å to about 5 Å, more preferably from 3 Å to about 4.5 Å, and mostpreferably from 3.5 Å to about 4.2 Å.

Molecular sieves, particularly zeolitic and zeolitic-type molecularsieves, preferably have a molecular framework of one, preferably two ormore corner-sharing [TO₄] tetrahedral units, more preferably, two ormore [SiO₄], [AlO₄] and/or [PO₄] tetrahedral units, and most preferably[SiO₄], [AlO₄] and [PO₄] tetrahedral units. These silicon, aluminum, andphosphorous based molecular sieves and metal containing silicon,aluminum and phosphorous based molecular sieves have been described indetail in numerous publications including for example, U.S. Pat. No.4,567,029 (MeAPO where Me is Mg, Mn, Zn, or Co), U.S. Pat. No. 4,440,871(SAPO), European Patent Application EP-A-0 159 624 (ELAPSO where El isAs, Be, B, Cr, Co, Ga, Ge, Fe, Li, Mg, Mn, Ti or Zn), U.S. Pat. No.4,554,143 (FeAPO), U.S. Pat. Nos. 4,822,478, 4,683,217, 4,744,885(FeAPSO), EP-A-0 158 975 and U.S. Pat. No. 4,935,216 (ZnAPSO, EP-A-0 161489 (CoAPSO), EP-A-0 158 976 (ELAPO, where EL is Co, Fe, Mg, Mn, Ti orZn), U.S. Pat. No. 4,310,440 (AlPO₄), EP-A-0 158 350 (SENAPSO), U.S.Pat. No. 4,973,460 (LiAPSO), U.S. Pat. No. 4,789,535 (LiAPO), U.S. Pat.No. 4,992,250 (GeAPSO), U.S. Pat. No. 4,888,167 (GeAPO), U.S. Pat. No.5,057,295 (BAPSO), U.S. Pat. No. 4,738,837 (CrAPSO), U.S. Pat. Nos.4,759,919, and 4,851,106 (CrAPO), U.S. Pat. Nos. 4,758,419, 4,882,038,5,434,326 and 5,478,787 (MgAPSO), U.S. Pat. No. 4,554,143 (FeAPO), U.S.Pat. No. 4,894,213 (AsAPSO), U.S. Pat. No. 4,913,888 (AsAPO), U.S. Pat.Nos. 4,686,092, 4,846,956 and 4,793,833 (MnAPSO), U.S. Pat. Nos.5,345,011 and 6,156,931 (MnAPO), U.S. Pat. No. 4,737,353 (BeAPSO), U.S.Pat. No. 4,940,570 (BeAPO), U.S. Pat. Nos. 4,801,309, 4,684,617 and4,880,520 (TiAPSO), U.S. Pat. Nos. 4,500,651, 4,551,236 and 4,605,492(TiAPO), U.S. Pat. Nos. 4,824,554, 4,744,970 (CoAPSO), U.S. Pat. No.4,735,806 (GaAPSO) EP-A-0 293 937 (QAPSO, where Q is framework oxideunit [QO₂]), as well as U.S. Pat. Nos. 4,567,029, 4,686,093, 4,781,814,4,793,984, 4,801,364, 4,853,197, 4,917,876, 4,952,384, 4,956,164,4,956,165, 4,973,785, 5,241,093, 5,493,066 and 5,675,050, all of whichare herein fully incorporated by reference.

Other molecular sieves include those described in EP-0 888 187 B1(microporous crystalline metallophosphates, SAPO₄ (UIO-6)), U.S. Pat.No. 6,004,898 (molecular sieve and an alkaline earth metal), U.S. patentapplication Ser. No. 09/511,943 filed Feb. 24, 2000 (integratedhydrocarbon co-catalyst), PCT WO 01/64340 published Sep. 7, 2001(thoriumcontaining molecular sieve), and R. Szostak, Handbook of MolecularSieves, Van Nostrand Reinhold, New York, N.Y. (1992), which are allherein fully incorporated by reference.

The more preferred silicon, aluminum and/or phosphorous containingmolecular sieves, and aluminum, phosphorous, and optionally silicon,containing molecular sieves include aluminophosphate (ALPO) molecularsieves and silicoaluminophosphate (SAPO) molecular sieves andsubstituted, preferably metal substituted, ALPO and SAPO molecularsieves. The most preferred molecular sieves are SAPO molecular sieves,and metal substituted SAPO molecular sieves. In an embodiment, the metalis an alkali metal of Group IA of the Periodic Table of Elements, analkaline earth metal of Group IIA of the Periodic Table of Elements, arare earth metal of Group IIIB, including the Lanthanides: lanthanum,cerium, praseodymium, neodymium, samarium, europium, gadolinium,terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium;and scandium or yttrium of the Periodic Table of Elements, a transitionmetal of Groups IVB, VB, VIB, VIIB, VIIIB, and IB of the Periodic Tableof Elements, or mixtures of any of these metal species. In one preferredembodiment, the metal is selected from the group consisting of Co, Cr,Cu, Fe, Ga, Ge, Mg, Mn, Ni, Sn, Ti, Zn and Zr, and mixtures thereof. Inanother preferred embodiment, these metal atoms discussed above areinserted into the framework of a molecular sieve through a tetrahedralunit, such as [MeO₂], and carry a net charge depending on the valencestate of the metal substituent. For example, in one embodiment, when themetal substituent has a valence state of +2, +3, +4, +5, or +6, the netcharge of the tetrahedral unit is between −2 and +2.

In one embodiment, the molecular sieve, as described in many of the U.S.Patents mentioned above, is represented by the empirical formula, on ananhydrous basis:

mR:(M_(x)Al_(y)P_(z))O₂

wherein R represents at least one templating agent, preferably anorganic templating agent; m is the number of moles of R per mole of(M_(x)Al_(y)P_(z))O₂ and m has a value from 0 to 1, preferably 0 to 0.5,and most preferably from 0 to 0.3; x, y, and z represent the molefraction of Al, P and M as tetrahedral oxides, where M is a metalselected from one of Group IA, IIA, IB, IIIB, IVB, VB, VIB, VIIB, VIIIBand Lanthanide's of the Periodic Table of Elements, preferably M isselected from one of the group consisting of Co, Cr, Cu, Fe, Ga, Ge, Mg,Mn, Ni, Sn, Ti, Zn and Zr. In an embodiment, m is greater than or equalto 0.2, and x, y and z are greater than or equal to 0.01.

In another embodiment, m is greater than 0.1 to about 1, x is greaterthan 0 to about 0.25, y is in the range of from 0.4 to 0.5, and z is inthe range of from 0.25 to 0.5, more preferably m is from 0.15 to 0.7, xis from 0.01 to 0.2, y is from 0.4 to 0.5, and z is from 0.3 to 0.5.

Non-limiting examples of SAPO and ALPO molecular sieves of the inventioninclude one or a combination of SAPO-5, SAPO-8, SAPO-11, SAPO-16,SAPO-17, SAPO-18, SAPO-20, SAPO-31, SAPO-34, SAPO-35, SAPO-36, SAPO-37,SAPO-40, SAPO-41, SAPO-42, SAPO-44 (U.S. Pat. No. 6,162,415), SAPO-47,SAPO-56, ALPO-5, ALPO-11, ALPO-18, ALPO-31, ALPO-34, ALPO-36, ALPO-37,ALPO-46, and metal containing molecular sieves thereof. The morepreferred zeolite-type molecular sieves include one or a combination ofSAPO-18, SAPO-34, SAPO-35, SAPO-44, SAPO-56, ALPO-18 and ALPO-34, evenmore preferably one or a combination of SAPO-18, SAPO-34, ALPO-34 andALPO-18, and metal containing molecular sieves thereof, and mostpreferably one or a combination of SAPO-34 and ALPO-18, and metalcontaining molecular sieves thereof.

In an embodiment, the molecular sieve is an intergrowth material havingtwo or more distinct phases of crystalline structures within onemolecular sieve composition. In particular, intergrowth molecular sievesare described in the U.S. patent application Ser. No. 09/924,016 filedAug. 7, 2001 and PCT WO 98/15496 published Apr. 16, 1998, both of whichare herein fully incorporated by reference. In another embodiment, themolecular sieve comprises at least one intergrown phase of AEI and CHAframework-types. For example, SAPO-18, ALPO-18 and RUW-18 have an AEIframework-type, and SAPO-34 has a CHA framework-type.

Molecular Sieve Synthesis

The synthesis of molecular sieves is described in many of the referencesdiscussed above. Generally, molecular sieves are synthesized by thehydrothermal crystallization of one or more of a source of aluminum, asource of phosphorous, a source of silicon, a templating agent, and ametal containing compound. Typically, a combination of sources ofsilicon, aluminum and phosphorous, optionally with one or moretemplating agents and/or one or more metal containing compounds areplaced in a sealed pressure vessel, optionally lined with an inertplastic such as polytetrafluoroethylene, and heated, under acrystallization pressure and temperature, until a crystalline materialis formed, and then recovered by filtration, centrifugation and/ordecanting.

In a preferred embodiment the molecular sieves are synthesized byforming a reaction product of a source of silicon, a source of aluminum,a source of phosphorous, an organic templating agent, preferably anitrogen containing organic templating agent, and one or more polymericbases. This particularly preferred embodiment results in the synthesisof a silicoaluminophosphate crystalline material that is then isolatedby filtration, centrifugation and/or decanting.

Non-limiting examples of silicon sources include a silicates, fumedsilica, for example, Aerosil-200 available from Degussa Inc., New York,N.Y., and CAB-O-SIL M-5, silicon compounds such as tetraalkylorthosilicates, for example, tetramethyl orthosilicate (TMOS) andtetraethylorthosilicate (TEOS), colloidal silicas or aqueous suspensionsthereof, for example Ludox-HS-40 sol available from E.I. du Pont deNemours, Wilmington, Del., silicic acid, alkali-metal silicate, or anycombination thereof. The preferred source of silicon is a silica sol.

Non-limiting examples of aluminum sources include aluminum-containingcompositions such as aluminum alkoxides, for example aluminumisopropoxide, aluminum phosphate, aluminum hydroxide, sodium aluminate,pseudo-boehmite, gibbsite and aluminum trichloride, or any combinationsthereof. A preferred source of aluminum is pseudo-boehmite, particularlywhen producing a silicoaluminophosphate molecular sieve.

Non-limiting examples of phosphorous sources, which may also includealuminum-containing phosphorous compositions, includephosphorous-containing, inorganic or organic, compositions such asphosphoric acid, organic phosphates such as triethyl phosphate, andcrystalline or amorphous aluminophosphates such as ALPO₄, phosphoroussalts, or combinations thereof. The preferred source of phosphorous isphosphoric acid, particularly when producing a silicoaluminophosphate.

Templating agents are generally compounds that contain elements of GroupVA of the Periodic Table of Elements, particularly nitrogen, phosphorus,arsenic and antimony, more preferably nitrogen or phosphorous, and mostpreferably nitrogen. Typical templating agents of Group VA of thePeriodic Table of elements also contain at least one alkyl or arylgroup, preferably an alkyl or aryl group having from 1 to 10 carbonatoms, and more preferably from 1 to 8 carbon atoms. The preferredtemplating agents are nitrogen-containing compounds such as amines andquaternary ammonium compounds.

The quaternary ammonium compounds, in one embodiment, are represented bythe general formula R₄N⁺, where each R is hydrogen or a hydrocarbyl orsubstituted hydrocarbyl group, preferably an alkyl group or an arylgroup having from 1 to 10 carbon atoms. In one embodiment, thetemplating agents include a combination of one or more quaternaryammonium compound(s) and one or more of a mono-, di- or tri- amine.

Non-limiting examples of templating agents include tetraalkyl ammoniumcompounds including salts thereof such as tetramethyl ammonium compoundsincluding salts thereof, tetraethyl ammonium compounds including saltsthereof, tetrapropyl ammonium including salts thereof, andtetrabutylammonium including salts thereof, cyclohexylamine, morpholine,di-n-propylamine (DPA), tripropylamine, triethylamine (TEA),triethanolamine, piperidine, cyclohexylamine, 2-methylpyridine,N,N-dimethylbenzylamine, N,N-diethylethanolamine, dicyclohexylamine,N,N-dimethylethanolamine, choline, N,N′-dimethylpiperazine,1,4-diazabicyclo(2,2,2)octane, N′,N′,N,N-tetramethyl(1,6)hexanediamine,N-methyldiethanolamine, N-methyl-ethanolamine, N-methyl piperidine,3-methyl-piperidine, N-methylcyclohexylamine, 3-methylpyridine,4-methyl-pyridine, quinuclidine, N,N′-dimethyl-1,4-diazabicyclo(2,2,2)octane ion; di-n-butylamine, neopentylamine, di-n-pentylamine,isopropylamine, t-butylamine, ethylenediamine, pyrrolidine, and2-imidazolidone.

The preferred templating agent or template is a tetraethylammoniumcompound, such as tetraethyl ammonium hydroxide (TEAOH), tetraethylammonium phosphate, tetraethyl ammonium fluoride, tetraethyl ammoniumbromide, tetraethyl ammonium chloride and tetraethyl ammonium acetate.The most preferred templating agent is tetraethyl ammonium hydroxide andsalts thereof, particularly when producing a silicoaluminophosphatemolecular sieve. In one embodiment, a combination of two or more of anyof the above templating agents is used in combination with one or moreof a silicon-, aluminum-, and phosphorous-source, and a polymeric base.

Polymeric bases, especially polymeric bases that are soluble ornon-ionic, useful in the invention, are those having a pH sufficient tocontrol the pH desired for synthesizing a given molecular sieve,especially a SAPO molecular sieve. In a preferred embodiment, thepolymeric base is soluble or the polymeric base is non-ionic, preferablythe polymeric base is a non-ionic and soluble polymeric base, and mostpreferably the polymeric base is a polymeric imine. In one embodiment,the polymeric base of the invention has a pH in an aqueous solution,preferably water, from greater than 7 to about 14, more preferably fromabout 8 to about 14, most preferably from about 9 to 14.

In another embodiment, the non-volatile polymeric base is represented bythe formula: (R—NH)_(x), where (R—NH) is a polymeric or monomeric unitwhere R contains from 1 to 20 carbon atoms, preferably from 1 to 10carbon atoms, more preferably from 1 to 6 carbon atoms, and mostpreferably from 1 to 4 carbon atoms; x is an integer from 1 to 500,000.In one embodiment, R is a linear, branched, or cyclic polymer,monomeric, chain, preferably a linear polymer chain having from 1 to 20carbon atoms.

In another embodiment, the polymeric base is a water miscible polymericbase, preferably in an aqueous solution. In yet another embodiment, thepolymeric base is a polyethylenimine that is represented by thefollowing general formula:

(—NHCH₂CH₂—)_(m)[—N(CH₂CH₂NH₂)CH₂CH₂—]_(n)),

wherein m is from 10 to 20,000, and n is from 0 to 2,000, preferablyfrom 1 to 2000.

In another embodiment, the polymeric base of the invention has a averagemolecular weight from about 500 to about 1,000,000, preferably fromabout 2,000 to about 800,000, more preferably from about 10,000 to about750,000, and most preferably from about 50,000 to about 750,000.

In another embodiment, the mole ratio of the monomeric unit of thepolymeric base of the invention, containing one basic group, to thetemplating agent(s) is less than 20, preferably less than 12, morepreferably less than 10, even more preferably less than 8, still evenmore preferably less than 5, and most preferably less than 4.

Non-limiting examples of polymer bases include: epichlorohydrin modifiedpolyethylenimine, ethoxylated polyethylenimine, polypropyleniminediamine dendrimers (DAB-Am-n), poly(allylamine) [CH₂CH(CH₂NH₂)]_(n),poly(1,2-dihydro-2,2,4-trimethylquinoline), andpoly(dimethylamine-co-epichlorohydrin-co-ethylenediamine).

In another embodiment the invention is directed to a method forsynthesizing a molecular sieve utilizing a templating agent, preferablyan organic templating agent such as an organic amine, an ammonium saltand/or an ammonium hydroxide, in combination with a polymeric base suchas polyethylenimine.

In a typical synthesis of the molecular sieve, the phosphorous-,aluminum-, and/or silicon-containing components are mixed, preferablywhile stirring and/or agitation and/or seeding with a crystallinematerial, optionally with an alkali metal, in a solvent such as water,and one or more templating agents and a polymeric base, to form asynthesis mixture that is then heated under crystallization conditionsof pressure and temperature as described in U.S. Pat. Nos. 4,440,871,4,861,743, 5,096,684, and 5,126,308, which are all herein fullyincorporated by reference. The polymeric base is combined with the atleast one templating agent, and one or more of the aluminum source,phosphorous source, and silicon source, in any order, for example,simultaneously with one or more of the sources, premixed with one ormore of the sources and/or templating agent, after combining the sourcesand the templating agent, and the like.

Generally, the synthesis mixture described above is sealed in a vesseland heated, preferably under autogenous pressure, to a temperature inthe range of from about 80° C. to about 250° C., preferably from about100° C. to about 250° C., more preferably from about 125° C. to about225° C., even more preferably from about 150° C. to about 180° C. Inanother embodiment, the hydrothermal crystallization temperature is lessthan 225° C., preferably less than 200° C. to about 80° C., and morepreferably less than 195° C. to about 100° C.

In yet another embodiment, the crystallization temperature is increasedgradually or stepwise during synthesis, preferably the crystallizationtemperature is maintained constant, for a period of time effective toform a crystalline product. The time required to form the crystallineproduct is typically from immediately up to several weeks, the durationof which is usually dependent on the temperature; the higher thetemperature the shorter the duration. In one embodiment, the crystallineproduct is formed under heating from about 30 minutes to around 2 weeks,preferably from about 45 minutes to about 240 hours, and more preferablyfrom about 1 hour to about 120 hours.

In one embodiment, the synthesis of a molecular sieve is aided by seedsfrom another or the same framework type molecular sieve.

The hydrothermal crystallization is carried out with or withoutagitation or stirring, for example stirring or tumbling. The stirring oragitation during the crystallization period may be continuous orintermittent, preferably continuous agitation. Typically, thecrystalline molecular sieve product is formed, usually in a slurrystate, and is recovered by any standard technique well known in the art,for example centrifugation or filtration. The isolated or separatedcrystalline product, in an embodiment, is washed, typically, using aliquid such as water, from one to many times. The washed crystallineproduct is then optionally dried, preferably in air.

One method for crystallization involves subjecting an aqueous reactionmixture containing an excess amount of a templating agent and polymericbase, subjecting the mixture to crystallization under hydrothermalconditions, establishing an equilibrium between molecular sieveformation and dissolution, and then, removing some of the excesstemplating agent and/or organic base to inhibit dissolution of themolecular sieve. See for example U.S. Pat. No. 5,296,208, which isherein fully incorporated by reference.

Another method of crystallization is directed to not stirring a reactionmixture, for example a reaction mixture containing at a minimum, asilicon-, an aluminum-, and/or a phosphorous-composition, with atemplating agent and a polymeric base, for a period of time duringcrystallization. See PCT WO 01/47810 published Jul. 5, 2001, which isherein fully incorporated by reference.

Other methods for synthesizing molecular sieves or modifying molecularsieves are described in U.S. Pat. No. 5,879,655 (controlling the ratioof the templating agent to phosphorous), U.S. Pat. No. 6,005,155 (use ofa modifier without a salt), U.S. Pat. No. 5,475,182 (acid extraction),U.S. Pat. No. 5,962,762 (treatment with transition metal), U.S. Pat.Nos. 5,925,586 and 6,153,552 (phosphorous modified), U.S. Pat. No.5,925,800 (monolith supported), U.S. Pat. No. 5,932,512 (fluorinetreated), U.S. Pat. No. 6,046,373 (electromagnetic wave treated ormodified), U.S. Pat. No. 6,051,746 (polynuclear aromatic modifier), U.S.Pat. No. 6,225,254 (heating template), PCT WO 01/36329 published May 25,2001 (surfactant synthesis), PCT WO 01/25151 published Apr. 12, 2001(staged acid addition), PCT WO 01/60746 published Aug. 23, 2001 (siliconoil), U.S. patent application Ser. No. 09/929,949 filed Aug. 15, 2001(cooling molecular sieve), U.S. patent application Ser. No. 09/615,526filed Jul. 13, 2000 (metal impregnation including copper), U.S. patentapplication Ser. No. 09/672,469 filed Sep. 28, 2000 (conductivemicrofilter), and U.S. patent application Ser. No. 09/754,812 filed Jan.4, 2001 (freeze drying the molecular sieve), which are all herein fullyincorporated by reference.

In one preferred embodiment, when a templating agent is used in thesynthesis of a molecular sieve, it is preferred that the templatingagent is substantially, preferably completely, removed aftercrystallization by numerous well known techniques, for example, heattreatments such as calcination. Calcination involves contacting themolecular sieve containing the templating agent with a gas, preferablycontaining oxygen, at any desired concentration at an elevatedtemperature sufficient to either partially or completely decompose andoxidize the templating agent.

Molecular sieve have either a high silicon (Si) to aluminum (Al) ratioor a low silicon to aluminum ratio, however, a low Si/Al ratio ispreferred for SAPO synthesis. In one embodiment, the molecular sieve hasa Si/Al ratio less than 0.65, preferably less than 0.40, more preferablyless than 0.32, and most preferably less than 0.20. In anotherembodiment the molecular sieve has a Si/Al ratio in the range of fromabout 0.65 to about 0.10, preferably from about 0.40 to about 0.10, morepreferably from about 0.32 to about 0.10, and more preferably from about0.32 to about 0.15.

The pH of a reaction mixture containing at a minimum a silicon-,aluminum-, and/or phosphorous-composition, a templating agent, and apolymeric base should be in the range of from 2 to 10, preferably in therange of from 4 to 9, and most preferably in the range of from 5 to 8.The pH can be controlled by the addition of basic or acidic compounds asnecessary to maintain the pH during the synthesis in the preferred rangeof from 4 to 9. In another embodiment, the templating agent and/orpolymeric base is added to the reaction mixture of the silicon sourceand phosphorous source such that the pH of the reaction mixture does notexceed 10.

In one embodiment, the molecular sieves of the invention are combinedwith one or more other molecular sieves. In another embodiment, thepreferred silicoaluminophosphate or aluminophosphate molecular sieves,or a combination thereof, are combined with one more of the followingnon-limiting examples of molecular sieves described in the following:Beta (U.S. Pat. No. 3,308,069), ZSM-5 (U.S. Pat. Nos. 3,702,886,4,797,267 and 5,783,321), ZSM-11 (U.S. Pat. No. 3,709,979), ZSM-12 (U.S.Pat. No. 3,832,449), ZSM-12 and ZSM-38 (U.S. Pat. No. 3,948,758), ZSM-22(U.S. Pat. No. 5,336,478), ZSM-23 (U.S. Pat. No. 4,076,842), ZSM-34(U.S. Pat. No. 4,086,186), ZSM-35 (U.S. Pat. No. 4,016,245, ZSM-48 (U.S.Pat. No. 4,397,827), ZSM-58 (U.S. Pat. No. 4,698,217), MCM-1 (U.S. Pat.No. 4,639,358), MCM-2 (U.S. Pat. No. 4,673,559), MCM-3 (U.S. Pat. No.4,632,811), MCM-4 (U.S. Pat. No. 4,664,897), MCM-5 (U.S. Pat. No.4,639,357), MCM-9 (U.S. Pat. No. 4,880,611), MCM-10 (U.S. Pat. No.4,623,527), MCM-14 (U.S. Pat. No. 4,619,818), MCM-22 (U.S. Pat. No.4,954,325), MCM-41 (U.S. Pat. No. 5,098,684), M-41S (U.S. Pat. No.5,102,643), MCM-48 (U.S. Pat. No. 5,198,203), MCM-49 (U.S. Pat. No.5,236,575), MCM-56 (U.S. Pat. No. 5,362,697), ALPO-11 (U.S. Pat. No.4,310,440), titanium aluminosilicates (TASO), TASO-45 (EP-A-0 229,-295),boron silicates (U.S. Pat. No. 4,254,297), titanium aluminophosphates(TAPO) (U.S. Pat. No. 4,500,651), mixtures of ZSM-5 and ZSM-11 (U.S.Pat. No. 4,229,424), ECR-18 (U.S. Pat. No. 5,278,345), SAPO-34 boundALPO-5 (U.S. Pat. No. 5,972,203), PCT WO 98/57743 published Dec. 23,1988 (molecular sieve and Fischer-Tropsch), U.S. Pat. No. 6,300,535(MFI-bound zeolites), and mesoporous molecular sieves (U.S. Pat. Nos.6,284,696, 5,098,684, 5,102,643 and 5,108,725), which are all hereinfully incorporated by reference.

Method for Making Molecular Sieve Catalyst Compositions

Once the molecular sieve is synthesized, depending on the requirementsof the particular conversion process, the molecular sieve is thenformulated into a molecular sieve catalyst composition, particularly forcommercial use. The molecular sieves synthesized above are made orformulated into catalysts by combining the synthesized molecular sieveswith a binder and/or a matrix material to form a molecular sievecatalyst composition or a formulated molecular sieve catalystcomposition. This formulated molecular sieve catalyst composition isformed into useful shape and sized particles by well-known techniquessuch as spray drying, pelletizing, extrusion, and the like.

There are many different binders that are useful in forming themolecular sieve catalyst composition. Non-limiting examples of bindersthat are useful alone or in combination include various types ofhydrated alumina, silicas, and/or other inorganic oxide sol. Onepreferred alumina containing sol is aluminum chlorhydrol. The inorganicoxide sol acts like glue binding the synthesized molecular sieves andother materials such as the matrix together, particularly after thermaltreatment. Upon heating, the inorganic oxide sol, preferably having alow viscosity, is converted into an inorganic oxide matrix component.For example, an alumina sol will convert to an aluminum oxide matrixfollowing heat treatment.

Aluminum chlorhydrol, a hydroxylated aluminum based sol containing achloride counter ion, has the general formula ofAl_(m)O_(n)(OH)_(o)Cl_(p).x(H₂O) wherein m is 1 to 20, n is 1 to 8, o is5 to 40, p is 2 to 15, and x is 0 to 30. In one embodiment, the binderis Al₁₃O₄(OH)₂₄Cl₇.12(H₂O) as is described in G. M. Wolterman, et al.,Stud. Surf. Sci. and Catal., 76, pages 105-144 (1993), which is hereinincorporated by reference. In another embodiment, one or more bindersare combined with one or more other non-limiting examples of aluminamaterials such as aluminum oxyhydroxide, γ-alumina, boehmite, diaspore,and transitional aluminas such as α-alumina, β-alumina, γ-alumina,δ-alumina, ε-alumina, κ-alumina, and ρ-alumina, aluminum trihydroxide,such as gibbsite, bayerite, nordstrandite, doyelite, and mixturesthereof.

In another embodiment, the binders are alumina sols, predominantlycomprising aluminum oxide, optionally including some silicon. In yetanother embodiment, the binders are peptized alumina made by treatingalumina hydrates such as pseudobohemite, with an acid, preferably anacid that does not contain a halogen, to prepare sols or aluminum ionsolutions. Non-limiting examples of commercially available colloidalalumina sols include Nalco 8676 available from Nalco Chemical Co.,Naperville, Ill., and Nyacol available from The PQ Corporation, ValleyForge, Pa.

The molecular sieve synthesized above, in a preferred embodiment, iscombined with one or more matrix material(s). Matrix materials aretypically effective in reducing overall catalyst cost, act as thermalsinks assisting in shielding heat from the catalyst composition forexample during regeneration, densifying the catalyst composition,increasing catalyst strength such as crush strength and attritionresistance, and to control the rate of conversion in a particularprocess.

Non-limiting examples of matrix materials include one or more of: rareearth metals, metal oxides including titania, zirconia, magnesia,thoria, beryllia, quartz, silica or sols, and mixtures thereof, forexample silica-magnesia, silica-zirconia, silica-titania, silica-aluminaand silica-alumina-thoria. In an embodiment, matrix materials arenatural clays such as those from the families of montmorillonite andkaolin. These natural clays include sabbentonites and those kaolinsknown as, for example, Dixie, McNamee, Georgia and Florida clays.Non-limiting examples of other matrix materials include: haloysite,kaolinite, dickite, nacrite, or anauxite. In one embodiment, the matrixmaterial, preferably any of the clays, are subjected to well knownmodification processes such as calcination and/or acid treatment and/orchemical treatment.

In one preferred embodiment, the matrix material is a clay or aclay-type composition, preferably the clay or clay-type compositionhaving a low iron or titania content, and most preferably the matrixmaterial is kaolin. Kaolin has been found to form a pumpable, high solidcontent slurry, it has a low fresh surface area, and it packs togethereasily due to its platelet structure. A preferred average particle sizeof the matrix material, most preferably kaolin, is from about 0.1 μm toabout 0.6 μm with a D90 particle size distribution of less than about 1μm.

In one embodiment, the binder, the molecular sieve and the matrixmaterial are combined in the presence of a liquid to form a molecularsieve catalyst composition, where the amount of binder is from about 2%by weight to about 30% by weight, preferably from about 5% by weight toabout 20% by weight, and more preferably from about 7% by weight toabout 15% by weight, based on the total weight of the binder, themolecular sieve and matrix material, excluding the liquid (aftercalcination).

In another embodiment, the weight ratio of the binder to the matrixmaterial used in the formation of the molecular sieve catalystcomposition is from 0:1 to 1:15, preferably 1:15 to 1:5, more preferably1:10 to 1:4, and most preferably 1:6 to 1:5. It has been found that ahigher sieve content, lower matrix content, increases the molecularsieve catalyst composition performance, however, lower sieve content,higher matrix material, improves the attrition resistance of thecomposition.

Upon combining the molecular sieve and the matrix material, optionallywith a binder, in a liquid to form a slurry, mixing, preferably rigorousmixing is needed to produce a substantially homogeneous mixturecontaining the molecular sieve. Non-limiting examples of suitableliquids include one or a combination of water, alcohol, ketones,aldehydes, and/or esters. The most preferred liquid is water. In oneembodiment, the slurry is colloid-milled for a period of time sufficientto produce the desired slurry texture, sub-particle size, and/orsub-particle size distribution.

The molecular sieve and matrix material, and the optional binder, are inthe same or different liquid, and are combined in any order, together,simultaneously, sequentially, or a combination thereof. In the preferredembodiment, the same liquid, preferably water is used. The molecularsieve, matrix material, and optional binder, are combined in a liquid assolids, substantially dry or in a dried form, or as slurries, togetheror separately. If solids are added together as dry or substantiallydried solids, it is preferable to add a limited and/or controlled amountof liquid.

In one embodiment, the slurry of the molecular sieve, binder and matrixmaterials is mixed or milled to achieve a sufficiently uniform slurry ofsub-particles of the molecular sieve catalyst composition that is thenfed to a forming unit that produces the molecular sieve catalystcomposition. In a preferred embodiment, the forming unit is spray dryer.Typically, the forming unit is maintained at a temperature sufficient toremove most of the liquid from the slurry, and from the resultingmolecular sieve catalyst composition. The resulting catalyst compositionwhen formed in this way takes the form of microspheres.

When a spray drier is used as the forming unit, typically, the slurry ofthe molecular sieve and matrix material, and optionally a binder, isco-fed to the spray drying volume with a drying gas with an averageinlet temperature ranging from 200° C. to 550° C., and a combined outlettemperature ranging from 100° C. to about 225° C. In an embodiment, theaverage diameter of the spray dried formed catalyst composition is fromabout 40 μm to about 300 μm, preferably from about 50 μm to about 250μm, more preferably from about 50 μm to about 200 μm, and mostpreferably from about 65 μm to about 90 μm.

During spray drying, the slurry is passed through a nozzle distributingthe slurry into small droplets, resembling an aerosol spray into adrying chamber. Atomization is achieved by forcing the slurry through asingle nozzle or multiple nozzles with a pressure drop in the range offrom 100 psia to 1000 psia (690 kPaa to 6895 kPaa). In anotherembodiment, the slurry is co-fed through a single nozzle or multiplenozzles along with an atomization fluid such as air, steam, flue gas, orany other suitable gas.

In yet another embodiment, the slurry described above is directed to theperimeter of a spinning wheel that distributes the slurry into smalldroplets, the size of which is controlled by many factors includingslurry viscosity, surface tension, flow rate, pressure, and temperatureof the slurry, the shape and dimension of the nozzle(s), or the spinningrate of the wheel. These droplets are then dried in a co-current orcounter-current flow of air passing through a spray drier to form asubstantially dried or dried molecular sieve catalyst composition, morespecifically a molecular sieve in powder form.

Generally, the size of the powder is controlled to some extent by thesolids content of the slurry. However, control of the size of thecatalyst composition and its spherical characteristics are controllableby varying the slurry feed properties and conditions of atomization.

Other methods for forming a molecular sieve catalyst composition isdescribed in U.S. patent application Ser. No. 09/617,714 filed Jul. 17,2000 (spray drying using a recycled molecular sieve catalystcomposition), which is herein incorporated by reference.

In another embodiment, the formulated molecular sieve catalystcomposition contains from about 1% to about 99%, more preferably fromabout 5% to about 90%, and most preferably from about 10% to about 80%,by weight of the molecular sieve based on the total weight of themolecular sieve catalyst composition.

In another embodiment, the weight percent of binder in or on the spraydried molecular sieve catalyst composition based on the total weight ofthe binder, molecular sieve, and matrix material is from about 2% byweight to about 30% by weight, preferably from about 5% by weight toabout 20% by weight, and more preferably from about 7% by weight toabout 15% by weight.

Once the molecular sieve catalyst composition is formed in asubstantially dry or dried state, to further harden and/or activate theformed catalyst composition, a heat treatment such as calcination, at anelevated temperature is usually performed. A conventional calcinationenvironment is air that typically includes a small amount of watervapor. Typical calcination temperatures are in the range from about 400°C. to about 1,000° C., preferably from about 500° C. to about 800° C.,and most preferably from about 550° C. to about 700° C., preferably in acalcination environment such as air, nitrogen, helium, flue gas(combustion product lean in oxygen), or any combination thereof.

In one embodiment, calcination of the formulated molecular sievecatalyst composition is carried out in any number of well known devicesincluding rotary calciners, fluid bed calciners, batch ovens, and thelike. Calcination time is typically dependent on the degree of hardeningof the molecular sieve catalyst composition and the temperature rangesfrom about 15 minutes to about 2 hours.

In a preferred embodiment, the molecular sieve catalyst composition isheated in nitrogen at a temperature of from about 600° C. to about 700°C. Heating is carried out for a period of time typically from 30 minutesto 15 hours, preferably from 1 hour to about 10 hours, more preferablyfrom about 1 hour to about 5 hours, and most preferably from about 2hours to about 4 hours.

Other methods for activating a molecular sieve catalyst composition, inparticular where the molecular sieve is a reaction product of thecombination of a silicon-, phosphorous-, and aluminum-sources, atemplating agent, and a polymeric base, more particularly asilicoaluminophosphate catalyst composition (SAPO) are described in, forexample, U.S. Pat. No. 5,185,310 (heating molecular sieve of gel aluminaand water to 450° C.), PCT WO 00/75072 published Dec. 14, 2000 (heatingto leave an amount of template), and U.S. application Ser. No.09/558,774 filed Apr. 26, 2000 (rejuvenation of molecular sieve), whichare all herein fully incorporated by reference.

Process for Using the Molecular Sieve Catalyst Compositions

The molecular sieve catalysts and compositions described above areuseful in a variety of processes including: cracking, of for example anaphtha feed to light olefin(s) (U.S. Pat. No. 6,300,537) or highermolecular weight (MW) hydrocarbons to lower MW hydrocarbons;hydrocracking, of for example heavy petroleum and/or cyclic feedstock;isomerization, of for example aromatics such as xylene, polymerization,of for example one or more olefin(s) to produce a polymer product;reforming; hydrogenation; dehydrogenation; dewaxing, of for examplehydrocarbons to remove straight chain paraffins; absorption, of forexample alkyl aromatic compounds for separating out isomers thereof;alkylation, of for example aromatic hydrocarbons such as benzene andalkyl benzene, optionally with propylene to produce cumeme or with longchain olefins; transalkylation, of for example a combination of aromaticand polyalkylaromatic hydrocarbons; dealkylation; hydrodecylization;disproportionation, of for example toluene to make benzene andparaxylene; oligomerization, of for example straight and branched chainolefin(s); and dehydrocyclization.

Preferred processes are conversion processes including: naphtha tohighly aromatic mixtures; light olefin(s) to gasoline, distillates andlubricants; oxygenates to olefin(s); light paraffins to olefins and/oraromatics; and unsaturated hydrocarbons (ethylene and/or acetylene) toaldehydes for conversion into alcohols, acids and esters. The mostpreferred process of the invention is a process directed to theconversion of a feedstock comprising one or more oxygenates to one ormore olefin(s).

The molecular sieve catalyst compositions described above areparticularly useful in conversion processes of different feedstock.Typically, the feedstock contains one or more aliphatic-containingcompounds that include alcohols, amines, carbonyl compounds for examplealdehydes, ketones and carboxylic acids, ethers, halides, mercaptans,sulfides, and the like, and mixtures thereof. The aliphatic moiety ofthe aliphatic-containing compounds typically contains from 1 to about 50carbon atoms, preferably from 1 to 20 carbon atoms, more preferably from1 to 10 carbon atoms, and most preferably from 1 to 4 carbon atoms.

Non-limiting examples of aliphatic-containing compounds include:alcohols such as methanol and ethanol, alkyl-mercaptans such as methylmercaptan and ethyl mercaptan, alkyl-sulfides such as methyl sulfide,alkyl-amines such as methyl amine, alkyl-ethers such as dimethyl ether,diethyl ether and methylethyl ether, alkyl-halides such as methylchloride and ethyl chloride, alkyl ketones such as dimethyl ketone,formaldehydes, and various acids such as acetic acid.

In a preferred embodiment of the process of the invention, the feedstockcontains one or more oxygenates, more specifically, one or more organiccompound(s) containing at least one oxygen atom. In the most preferredembodiment of the process of invention, the oxygenate in the feedstockis one or more alcohol(s), preferably aliphatic alcohol(s) where thealiphatic moiety of the alcohol(s) has from 1 to 20 carbon atoms,preferably from 1 to 10 carbon atoms, and most preferably from 1 to 4carbon atoms. The alcohols useful as feedstock in the process of theinvention include lower straight and branched chain aliphatic alcoholsand their unsaturated counterparts.

Non-limiting examples of oxygenates include methanol, ethanol,n-propanol, isopropanol, methyl ethyl ether, dimethyl ether, diethylether, di-isopropyl ether, formaldehyde, dimethyl carbonate, dimethylketone, acetic acid, and mixtures thereof.

In the most preferred embodiment, the feedstock is selected from one ormore of methanol, ethanol, dimethyl ether, diethyl ether or acombination thereof, more preferably methanol and dimethyl ether, andmost preferably methanol.

The various feedstocks discussed above, particularly a feedstockcontaining an oxygenate, more particularly a feedstock containing analcohol, is converted primarily into one or more olefin(s). Theolefin(s) or olefin monomer(s) produced from the feedstock typicallyhave from 2 to 30 carbon atoms, preferably 2 to 8 carbon atoms, morepreferably 2 to 6 carbon atoms, still more preferably 2 to 4 carbonsatoms, and most preferably ethylene an/or propylene.

Non-limiting examples of olefin monomer(s) include ethylene, propylene,butene-1, pentene-1, 4-methyl-pentene-1, hexene-1, octene-1 anddecene-1, preferably ethylene, propylene, butene-1, pentene-1,4-methyl-pentene-1, hexene-1, octene-1 and isomers thereof. Other olefinmonomer(s) include unsaturated monomers, diolefins having 4 to 18 carbonatoms, conjugated or nonconjugated dienes, polyenes, vinyl monomers andcyclic olefins.

In the most preferred embodiment, the feedstock, preferably of one ormore oxygenates, is converted in the presence of a molecular sievecatalyst composition into olefin(s) having 2 to 6 carbons atoms,preferably 2 to 4 carbon atoms. Most preferably, the olefin(s), alone orcombination, are converted from a feedstock containing an oxygenate,preferably an alcohol, most preferably methanol, to the preferredolefin(s) ethylene and/or propylene.

The are many processes used to convert feedstock into olefin(s)including various cracking processes such as steam cracking, thermalregenerative cracking, fluidized bed cracking, fluid catalytic cracking,deep catalytic cracking, and visbreaking.

The most preferred process is generally referred to as gas-to-olefins(GTO) or alternatively, methanol-to-olefins (MTO). In a MTO process,typically an oxygenated feedstock, most preferably a methanol containingfeedstock, is converted in the presence of a molecular sieve catalystcomposition into one or more olefin(s), preferably and predominantly,ethylene and/or propylene, often referred to as light olefin(s).

In one embodiment of the process for conversion of a feedstock,preferably a feedstock containing one or more oxygenates, the amount ofolefin(s) produced based on the total weight of hydrocarbon produced isgreater than 50 weight percent, preferably greater than 60 weightpercent, more preferably greater than 70 weight percent, and mostpreferably greater than 75 weight percent. In another embodiment of theprocess for conversion of one or more oxygenates to one or moreolefin(s), the amount of ethylene and/or propylene produced based on thetotal weight of hydrocarbon product produced is greater than 65 weightpercent, preferably greater than 70 weight percent, more preferablygreater than 75 weight percent, and most preferably greater than 78weight percent.

In another embodiment of the process for conversion of one or moreoxygenates to one or more olefin(s), the amount ethylene produced inweight percent based on the total weight of hydrocarbon productproduced, is greater than 30 weight percent, more preferably greaterthan 35 weight percent, and most preferably greater than 40 weightpercent. In yet another embodiment of the process for conversion of oneor more oxygenates to one or more olefin(s), the amount of propyleneproduced in weight percent based on the total weight of hydrocarbonproduct produced is greater than 20 weight percent, preferably greaterthan 25 weight percent, more preferably greater than 30 weight percent,and most preferably greater than 35 weight percent.

Increasing the selectivity of preferred hydrocarbon products such asethylene and/or propylene from the conversion of an oxygenate using amolecular sieve catalyst composition is described in U.S. Pat. No.6,137,022 (linear velocity), and PCT WO 00/74848 published Dec. 14, 2000(methanol uptake index of at least 0.13), which are all herein fullyincorporated by reference.

The feedstock, in one embodiment, contains one or more diluent(s),typically used to reduce the concentration of the feedstock, and aregenerally non-reactive to the feedstock or molecular sieve catalystcomposition. Non-limiting examples of diluents include helium, argon,nitrogen, carbon monoxide, carbon dioxide, water, essentiallynon-reactive paraffins (especially alkanes such as methane, ethane, andpropane), essentially non-reactive aromatic compounds, and mixturesthereof. The most preferred diluents are water and nitrogen, with waterbeing particularly preferred.

The diluent, water, is used either in a liquid or a vapor form, or acombination thereof. The diluent is either added directly to a feedstockentering into a reactor or added directly into a reactor, or added witha molecular sieve catalyst composition. In one embodiment, the amount ofdiluent in the feedstock is in the range of from about 1 to about 99mole percent based on the total number of moles of the feedstock anddiluent, preferably from about 1 to 80 mole percent, more preferablyfrom about 5 to about 50, most preferably from about 5 to about 25. Inone embodiment, other hydrocarbons are added to a feedstock eitherdirectly or indirectly, and include olefin(s), paraffin(s), aromatic(s)(see for example U.S. Pat. No. 4,677,242, addition of aromatics) ormixtures thereof, preferably propylene, butylene, pentylene, and otherhydrocarbons having 4 or more carbon atoms, or mixtures thereof.

The process for converting a feedstock, especially a feedstockcontaining one or more oxygenates, in the presence of a molecular sievecatalyst composition of the invention, is carried out in a reactionprocess in a reactor, where the process is a fixed bed process, afluidized bed process (includes a turbulent bed process), preferably acontinuous fluidized bed process, and most preferably a continuous highvelocity fluidized bed process.

The reaction processes can take place in a variety of catalytic reactorssuch as hybrid reactors that have a dense bed or fixed bed reactionzones and/or fast fluidized bed reaction zones coupled together,circulating fluidized bed reactors, riser reactors, and the like.Suitable conventional reactor types are described in for example U.S.Pat. No. 4,076,796, U.S. Pat. No. 6,287,522 (dual riser), andFluidization Engineering, D. Kunii and O. Levenspiel, Robert E. KriegerPublishing Company, New York, N.Y. 1977, which are all herein fullyincorporated by reference.

The preferred reactor type are riser reactors generally described inRiser Reactor, Fluidization and Fluid-Particle Systems, pages 48 to 59,F. A. Zenz and D. F. Othmo, Reinhold Publishing Corporation, New York,1960, and U.S. Pat. No. 6,166,282 (fast-fluidized bed reactor), and U.S.patent application Ser. No. 09/564,613 filed May 4, 2000 (multiple riserreactor), which are all herein fully incorporated by reference.

In the preferred embodiment, a fluidized bed process or high velocityfluidized bed process includes a reactor system, a regeneration systemand a recovery system.

The reactor system preferably is a fluid bed reactor system having afirst reaction zone within one or more riser reactor(s) and a secondreaction zone within at least one disengaging vessel, preferablycomprising one or more cyclones. In one embodiment, the one or moreriser reactor(s) and disengaging vessel is contained within a singlereactor vessel. Fresh feedstock, preferably containing one or moreoxygenates, optionally with one or more diluent(s), is fed to the one ormore riser reactor(s) in which a zeolite or zeolite-type molecular sievecatalyst composition or coked version thereof is introduced. In oneembodiment, the molecular sieve catalyst composition or coked versionthereof is contacted with a liquid or gas, or combination thereof, priorto being introduced to the riser reactor(s), preferably the liquid iswater or methanol, and the gas is an inert gas such as nitrogen.

In an embodiment, the amount of fresh feedstock fed separately orjointly with a vapor feedstock, to a reactor system is in the range offrom 0.1 weight percent to about 85 weight percent, preferably fromabout 1 weight percent to about 75 weight percent, more preferably fromabout 5 weight percent to about 65 weight percent based on the totalweight of the feedstock including any diluent contained therein. Theliquid and vapor feedstocks are preferably the same composition, orcontain varying proportions of the same or different feedstock with thesame or different diluent.

The feedstock entering the reactor system is preferably converted,partially or fully, in the first reactor zone into a gaseous effluentthat enters the disengaging vessel along with a coked molecular sievecatalyst composition. In the preferred embodiment, cyclone(s) within thedisengaging vessel are designed to separate the molecular sieve catalystcomposition, preferably a coked molecular sieve catalyst composition,from the gaseous effluent containing one or more olefin(s) within thedisengaging zone. Cyclones are preferred, however, gravity effectswithin the disengaging vessel will also separate the catalystcompositions from the gaseous effluent. Other methods for separating thecatalyst compositions from the gaseous effluent include the use ofplates, caps, elbows, and the like.

In one embodiment of the disengaging system, the disengaging systemincludes a disengaging vessel, typically a lower portion of thedisengaging vessel is a stripping zone. In the stripping zone the cokedmolecular sieve catalyst composition is contacted with a gas, preferablyone or a combination of steam, methane, carbon dioxide, carbon monoxide,hydrogen, or an inert gas such as argon, preferably steam, to recoveradsorbed hydrocarbons from the coked molecular sieve catalystcomposition that is then introduced to the regeneration system. Inanother embodiment, the stripping zone is in a separate vessel from thedisengaging vessel and the gas is passed at a gas hourly superficialvelocity (GHSV) of from 1 hr⁻¹ to about 20,000 hr⁻¹ based on the volumeof gas to volume of coked molecular sieve catalyst composition,preferably at an elevated temperature from 250° C. to about 750° C.,preferably from about 350° C. to 650° C., over the coked molecular sievecatalyst composition.

The conversion temperature employed in the conversion process,specifically within the reactor system, is in the range of from about200° C. to about 1000° C., preferably from about 250° C. to about 800°C., more preferably from about 250° C. to about 750° C., yet morepreferably from about 300° C. to about 650° C., yet even more preferablyfrom about 350° C. to about 600° C. most preferably from about 350° C.to about 550° C.

The conversion pressure employed in the conversion process, specificallywithin the reactor system, varies over a wide range including autogenouspressure. The conversion pressure is based on the partial pressure ofthe feedstock exclusive of any diluent therein. Typically the conversionpressure employed in the process is in the range of from about 0.1 kPaato about 5 MPaa, preferably from about 5 kPaa to about 1 MPaa, and mostpreferably from about 20 kPaa to about 500 kPaa.

The weight hourly space velocity (WHSV), particularly in a process forconverting a feedstock containing one or more oxygenates in the presenceof a molecular sieve catalyst composition within a reaction zone, isdefined as the total weight of the feedstock excluding any diluents tothe reaction zone per hour per weight of molecular sieve in themolecular sieve catalyst composition in the reaction zone. The WHSV ismaintained at a level sufficient to keep the catalyst composition in afluidized state within a reactor.

Typically, the WHSV ranges from about 1 hr⁻¹ to about 5000 hr⁻¹,preferably from about 2 hr⁻¹ to about 3000 hr⁻¹, more preferably fromabout 5 hr⁻¹ to about 1500 hr⁻¹, and most preferably from about 10 hr⁻¹to about 1000 hr⁻¹. In one preferred embodiment, the WHSV is greaterthan 20 hr⁻¹, preferably the WHSV for conversion of a feedstockcontaining methanol and dimethyl ether is in the range of from about 20hr⁻¹ to about 300 hr⁻¹.

The superficial gas velocity (SGV) of the feedstock including diluentand reaction products within the reactor system is preferably sufficientto fluidize the molecular sieve catalyst composition within a reactionzone in the reactor. The SGV in the process, particularly within thereactor system, more particularly within the riser reactor(s), is atleast 0.1 meter per second (m/sec), preferably greater than 0.5 m/sec,more preferably greater than 1 m/sec, even more preferably greater than2 m/sec, yet even more preferably greater than 3 m/sec, and mostpreferably greater than 4 m/sec. See for example U.S. patent applicationSer. No. 09/708,753 filed Nov. 8, 2000, which is herein incorporated byreference.

In one preferred embodiment of the process for converting an oxygenateto olefin(s) using a silicoaluminophosphate molecular sieve catalystcomposition, the process is operated at a WHSV of at least 20 hr⁻¹ and aTemperature Corrected Normalized Methane Selectivity (TCNMS) of lessthan 0.016, preferably less than or equal to 0.01. See for example U.S.Pat. No. 5,952,538, which is herein fully incorporated by reference.

In another embodiment of the processes for converting an oxygenate suchas methanol to one or more olefin(s) using a molecular sieve catalystcomposition, the WHSV is from 0.01 hr⁻¹ to about 100 hr⁻¹, at atemperature of from about 350° C. to 550° C., and silica to Me₂O₃ (Me isa Group IIIA or VIII element from the Periodic Table of Elements) molarratio of from 300 to 2500. See for example EP-0 642 485 B1, which isherein fully incorporated by reference.

Other processes for converting an oxygenate such as methanol to one ormore olefin(s) using a molecular sieve catalyst composition aredescribed in PCT WO 01/23500 published Apr. 5, 2001 (propane reductionat an average catalyst feedstock exposure of at least 1.0), which isherein incorporated by reference.

The coked molecular sieve catalyst composition is withdrawn from thedisengaging vessel, preferably by one or more cyclones(s), andintroduced to the regeneration system. The regeneration system comprisesa regenerator where the coked catalyst composition is contacted with aregeneration medium, preferably a gas containing oxygen, under generalregeneration conditions of temperature, pressure and residence time.

Non-limiting examples of the regeneration medium include one or more ofoxygen, O₃, SO₃, N₂O, NO, NO₂, N₂O₅, air, air diluted with nitrogen orcarbon dioxide, oxygen and water (U.S. Pat. No. 6,245,703), carbonmonoxide and/or hydrogen. The regeneration conditions are those capableof burning coke from the coked catalyst composition, preferably to alevel less than 0.5 weight percent based on the total weight of thecoked molecular sieve catalyst composition entering the regenerationsystem. The coked molecular sieve catalyst composition withdrawn fromthe regenerator forms a regenerated molecular sieve catalystcomposition.

The regeneration temperature is in the range of from about 200° C. toabout 1500° C., preferably from about 300° C. to about 1000° C., morepreferably from about 450° C. to about 750° C., and most preferably fromabout 550° C. to 700° C. The regeneration pressure is in the range offrom about 15 psia (103 kPaa) to about 500 psia (3448 kPaa), preferablyfrom about 20 psia (138 kPaa) to about 250 psia (1724 kPaa), morepreferably from about 25 psia (172 kPaa) to about 150 psia (1034 kPaa),and most preferably from about 30 psia (207 kPaa) to about 60 psia (414kPaa).

The preferred residence time of the molecular sieve catalyst compositionin the regenerator is in the range of from about one minute to severalhours, most preferably about one minute to 100 minutes, and thepreferred volume of oxygen in the gas is in the range of from about 0.01mole percent to about 5 mole percent based on the total volume of thegas.

In one embodiment, regeneration promoters, typically metal containingcompounds such as platinum, palladium and the like, are added to theregenerator directly, or indirectly, for example with the coked catalystcomposition. Also, in another embodiment, a fresh molecular sievecatalyst composition is added to the regenerator containing aregeneration medium of oxygen and water as described in U.S. Pat. No.6,245,703, which is herein fully incorporated by reference.

In an embodiment, a portion of the coked molecular sieve catalystcomposition from the regenerator is returned directly to the one or moreriser reactor(s), or indirectly, by pre-contacting with the feedstock,or contacting with fresh molecular sieve catalyst composition, orcontacting with a regenerated molecular sieve catalyst composition or acooled regenerated molecular sieve catalyst composition described below.

The burning of coke is an exothermic reaction, and in an embodiment, thetemperature within the regeneration system is controlled by varioustechniques in the art including feeding a cooled gas to the regeneratorvessel, operated either in a batch, continuous, or semi-continuous mode,or a combination thereof. A preferred technique involves withdrawing theregenerated molecular sieve catalyst composition from the regenerationsystem and passing the regenerated molecular sieve catalyst compositionthrough a catalyst cooler that forms a cooled regenerated molecularsieve catalyst composition. The catalyst cooler, in an embodiment, is aheat exchanger that is located either internal or external to theregeneration system.

In one embodiment, the cooler regenerated molecular sieve catalystcomposition is returned to the regenerator in a continuous cycle,alternatively, (see U.S. patent application Ser. No. 09/587,766 filedJun. 6, 2000) a portion of the cooled regenerated molecular sievecatalyst composition is returned to the regenerator vessel in acontinuous cycle, and another portion of the cooled molecular sieveregenerated molecular sieve catalyst composition is returned to theriser reactor(s), directly or indirectly, or a portion of theregenerated molecular sieve catalyst composition or cooled regeneratedmolecular sieve catalyst composition is contacted with by-productswithin the gaseous effluent (PCT WO 00/49106 published Aug. 24, 2000),which are all herein fully incorporated by reference. In anotherembodiment, a regenerated molecular sieve catalyst composition contactedwith an alcohol, preferably ethanol, 1-propnaol, 1-butanol or mixturethereof, is introduced to the reactor system, as described in U.S.patent application Ser. No. 09/785,122 filed Feb. 16, 2001, which isherein fully incorporated by reference.

Other methods for operating a regeneration system are in disclosed U.S.Pat. No. 6,290,916 (controlling moisture), which is herein fullyincorporated by reference.

The regenerated molecular sieve catalyst composition withdrawn from theregeneration system, preferably from the catalyst cooler, is combinedwith a fresh molecular sieve catalyst composition and/or re-circulatedmolecular sieve catalyst composition and/or feedstock and/or fresh gasor liquids, and returned to the riser reactor(s). In another embodiment,the regenerated molecular sieve catalyst composition withdrawn from theregeneration system is returned to the riser reactor(s) directly,preferably after passing through a catalyst cooler. In one embodiment, acarrier, such as an inert gas, feedstock vapor, steam or the like,semi-continuously or continuously, facilitates the introduction of theregenerated molecular sieve catalyst composition to the reactor system,preferably to the one or more riser reactor(s).

By controlling the flow of the regenerated molecular sieve catalystcomposition or cooled regenerated molecular sieve catalyst compositionfrom the regeneration system to the reactor system, the optimum level ofcoke on the molecular sieve catalyst composition entering the reactor ismaintained. There are many techniques for controlling the flow of amolecular sieve catalyst composition described in Michael Louge,Experimental Techniques, Circulating Fluidized Beds, Grace, Avidan andKnowlton, eds., Blackie, 1997 (336-337), which is herein incorporated byreference.

Coke levels on the molecular sieve catalyst composition is measured bywithdrawing from the conversion process the molecular sieve catalystcomposition at a point in the process and determining its carboncontent. Typical levels of coke on the molecular sieve catalystcomposition, after regeneration is in the range of from 0.01 weightpercent to about 15 weight percent, preferably from about 0.1 weightpercent to about 10 weight percent, more preferably from about 0.2weight percent to about 5 weight percent, and most preferably from about0.3 weight percent to about 2 weight percent based on the total weightof the molecular sieve and not the total weight of the molecular sievecatalyst composition.

In one preferred embodiment, the mixture of fresh molecular sievecatalyst composition and regenerated molecular sieve catalystcomposition and/or cooled regenerated molecular sieve catalystcomposition contains in the range of from about 1 to 50 weight percent,preferably from about 2 to 30 weight percent, more preferably from about2 to about 20 weight percent, and most preferably from about 2 to about10 coke or carbonaceous deposit based on the total weight of the mixtureof molecular sieve catalyst compositions. See for example U.S. Pat. No.6,023,005, which is herein fully incorporated by reference.

The gaseous effluent is withdrawn from the disengaging system and ispassed through a recovery system. There are many well known recoverysystems, techniques and sequences that are useful in separatingolefin(s) and purifying olefin(s) from the gaseous effluent. Recoverysystems generally comprise one or more or a combination of a variousseparation, fractionation and/or distillation towers, columns,splitters, or trains, reaction systems such as ethylbenzene manufacture(U.S. Pat. No. 5,476,978) and other derivative processes such asaldehydes, ketones and ester manufacture (U.S. Pat. No. 5,675,041), andother associated equipment for example various condensers, heatexchangers, refrigeration systems or chill trains, compressors,knock-out drums or pots, pumps, and the like.

Non-limiting examples of these towers, columns, splitters or trains usedalone or in combination include one or more of a demethanizer,preferably a high temperature demethanizer, a dethanizer, adepropanizer, preferably a wet depropanizer, a wash tower often referredto as a caustic wash tower and/or quench tower, absorbers, adsorbers,membranes, ethylene (C2) splitter, propylene (C3) splitter, butene (C4)splitter, and the like.

Various recovery systems useful for recovering predominately olefin(s),preferably prime or light olefin(s) such as ethylene, propylene and/orbutene are described in U.S. Pat. No. 5,960,643 (secondary rich ethylenestream), U.S. Pat. Nos. 5,019,143, 5,452,581 and 5,082,481 (membraneseparations), U.S. Pat. No. 5,672,197 (pressure dependent adsorbents),U.S. Pat. No. 6,069,288 (hydrogen removal), U.S. Pat. No. 5,904,880(recovered methanol to hydrogen and carbon dioxide in one step), U.S.Pat. No. 5,927,063 (recovered methanol to gas turbine power plant), andU.S. Pat. No. 6,121,504 (direct product quench), U.S. Pat. No. 6,121,503(high purity olefins without superfractionation), and U.S. Pat. No.6,293,998 (pressure swing adsorption), which are all herein fullyincorporated by reference.

Generally accompanying most recovery systems is the production,generation or accumulation of additional products, by-products and/orcontaminants along with the preferred prime products. The preferredprime products, the light olefins, such as ethylene and propylene, aretypically purified for use in derivative manufacturing processes such aspolymerization processes. Therefore, in the most preferred embodiment ofthe recovery system, the recovery system also includes a purificationsystem. For example, the light olefin(s) produced particularly in a MTOprocess are passed through a purification system that removes low levelsof by-products or contaminants.

Non-limiting examples of contaminants and by-products include generallypolar compounds such as water, alcohols, carboxylic acids, ethers,carbon oxides, sulfur compounds such as hydrogen sulfide, carbonylsulfides and mercaptans, ammonia and other nitrogen compounds, arsine,phosphine and chlorides. Other contaminants or by-products includehydrogen and hydrocarbons such as acetylene, methyl acetylene,propadiene, butadiene and butyne.

Other recovery systems that include purification systems, for examplefor the purification of olefin(s), are described in Kirk-OthmerEncyclopedia of Chemical Technology, 4th Edition, Volume 9, John Wiley &Sons, 1996, pages 249-271 and 894-899, which is herein incorporated byreference. Purification systems are also described in for example, U.S.Pat. No. 6,271,428 (purification of a diolefin hydrocarbon stream), U.S.Pat. No. 6,293,999 (separating propylene from propane), and U.S. patentapplication Ser. No. 09/689,363 filed Oct. 20, 2000 (purge stream usinghydrating catalyst), which is herein incorporated by reference.

Typically, in converting one or more oxygenates to olefin(s) having 2 or3 carbon atoms, an amount of hydrocarbons, particularly olefin(s),especially olefin(s) having 4 or more carbon atoms, and otherby-products are formed or produced. Included in the recovery systems ofthe invention are reaction systems for converting the products containedwithin the effluent gas withdrawn from the reactor or converting thoseproducts produced as a result of the recovery system utilized.

In one embodiment, the effluent gas withdrawn from the reactor is passedthrough a recovery system producing one or more hydrocarbon containingstream(s), in particular, a three or more carbon atom (C₃ ⁺) hydrocarboncontaining stream. In this embodiment, the C₃ ⁺ hydrocarbon containingstream is passed through a first fractionation zone producing a crude C₃hydrocarbon and a C₄ ⁺ hydrocarbon containing stream, the C₄ ⁺hydrocarbon containing stream is passed through a second fractionationzone producing a crude C₄ hydrocarbon and a C₅ ⁺ hydrocarbon containingstream. The four or more carbon hydrocarbons include butenes such asbutene-1 and butene-2, butadienes, saturated butanes, and isobutanes.

The effluent gas removed from a conversion process, particularly a MTOprocess, typically has a minor amount of hydrocarbons having 4 or morecarbon atoms. The amount of hydrocarbons having 4 or more carbon atomsis typically in an amount less than 20 weight percent, preferably lessthan 10 weight percent, more preferably less than 5 weight percent, andmost preferably less than 2 weight percent, based on the total weight ofthe effluent gas withdrawn from a MTO process, excluding water. Inparticular with a conversion process of oxygenates into olefin(s)utilizing a molecular sieve catalyst composition the resulting effluentgas typically comprises a majority of ethylene and/or propylene and aminor amount of four carbon and higher carbon number products and otherby-products, excluding water.

Suitable well known reaction systems as part of the recovery systemprimarily take lower value products and convert them to higher valueproducts. For example, the C₄ hydrocarbons, butene-1 and butene-2 areused to make alcohols having 8 to 13 carbon atoms, and other specialtychemicals, isobutylene is used to make a gasoline additive,methyl-t-butylether, butadiene in a selective hydrogenation unit isconverted into butene-1 and butene-2, and butane is useful as a fuel.

Non-limiting examples of reaction systems include U.S. Pat. No.5,955,640 (converting a four carbon product into butene-1), U.S. Pat.No. 4,774,375 (isobutane and butene-2 oligomerized to an alkylategasoline), U.S. Pat. No. 6,049,017 (dimerization of n-butylene), U.S.Pat. Nos. 4,287,369 and 5,763,678 (carbonylation or hydroformulation ofhigher olefins with carbon dioxide and hydrogen making carbonylcompounds), U.S. Pat. No. 4,542,252 (multistage adiabatic process), U.S.Pat. No. 5,634,354 (olefin-hydrogen recovery), and Cosyns, J. et al.,Process for Upgrading C3, C4 and C5 Olefinic Streams, Pet. & Coal, Vol.37, No. 4 (1995) (dimerizing or oligomerizing propylene, butylene andpentylene), which are all herein fully incorporated by reference.

The preferred light olefin(s) produced by any one of the processesdescribed above, preferably conversion processes, are high purity primeolefin(s) products that contains a single carbon number olefin in anamount greater than 80 percent, preferably greater than 90 weightpercent, more preferably greater than 95 weight percent, and mostpreferably no less than about 99 weight percent, based on the totalweight of the olefin.

In one embodiment, high purity prime olefin(s) are produced in theprocess of the invention at rate of greater than 5 kg per day,preferably greater than 10 kg per day, more preferably greater than 20kg per day, and most preferably greater than 50 kg per day. In anotherembodiment, high purity ethylene and/or high purity propylene isproduced by the process of the invention at a rate greater than 4,500 kgper day, preferably greater than 100,000 kg per day, more preferablygreater than 500,000 kg per day, even more preferably greater than1,000,000 kg per day, yet even more preferably greater than 1,500,000 kgper day, still even more preferably greater than 2,000,000 kg per day,and most preferably greater than 2,500,000 kg per day.

Other conversion processes, in particular, a conversion process of anoxygenate to one or more olefin(s) in the presence of a molecular sievecatalyst composition, especially where the molecular sieve issynthesized from a silicon-, phosphorous-, and alumina-source, includethose described in for example: U.S. Pat. No. 6,121,503 (making plasticwith an olefin product having a paraffin to olefin weight ratio lessthan or equal to 0.05), U.S. Pat. No. 6,187,983 (electromagnetic energyto reaction system), PCT WO 99/18055 publishes Apr. 15, 1999 (heavyhydrocarbon in effluent gas fed to another reactor) PCT WO 01/60770published Aug. 23, 2001 and U.S. patent application Ser. No. 09/627,634filed Jul. 28, 2000 (high pressure), U.S. patent application Ser. No.09/507,838 filed Feb. 22, 2000 (staged feedstock injection), and U.S.patent application Ser. No. 09/785,409 filed Feb. 16, 2001 (acetoneco-fed), which are all herein fully incorporated by reference.

In an embodiment, an integrated process is directed to producing lightolefin(s) from a hydrocarbon feedstock, preferably a hydrocarbon gasfeedstock, more preferably methane and/or ethane. The first step in theprocess is passing the gaseous feedstock, preferably in combination witha water stream, to a syngas production zone to produce a synthesis gas(syngas) stream. Syngas production is well known, and typical syngastemperatures are in the range of from about 700° C. to about 1200° C.and syngas pressures are in the range of from about 2 MPa to about 100MPa. Synthesis gas streams are produced from natural gas, petroleumliquids, and carbonaceous materials such as coal, recycled plastic,municipal waste or any other organic material, preferably synthesis gasstream is produced via steam reforming of natural gas.

Generally, a heterogeneous catalyst, typically a copper based catalyst,is contacted with a synthesis gas stream, typically carbon dioxide andcarbon monoxide and hydrogen to produce an alcohol, preferably methanol,often in combination with water. In one embodiment, the synthesis gasstream at a synthesis temperature in the range of from about 150° C. toabout 450° C. and at a synthesis pressure in the range of from about 5MPa to about 10 MPa is passed through a carbon oxide conversion zone toproduce an oxygenate containing stream.

This oxygenate containing stream, or crude methanol, typically containsthe alcohol product and various other components such as ethers,particularly dimethyl ether, ketones, aldehydes, dissolved gases such ashydrogen methane, carbon oxide and nitrogen, and fusel oil. Theoxygenate containing stream, crude methanol, in the preferred embodimentis passed through a well known purification processes, distillation,separation and fractionation, resulting in a purified oxygenatecontaining stream, for example, commercial Grade A and AA methanol.

The oxygenate containing stream or purified oxygenate containing stream,optionally with one or more diluents, is contacted with one or moremolecular sieve catalyst composition described above in any one of theprocesses described above to produce a variety of prime products,particularly light olefin(s), ethylene and/or propylene. Non-limitingexamples of this integrated process is described in EP-B-0 933 345,which is herein fully incorporated by reference.

In another more fully integrated process, optionally with the integratedprocesses described above, olefin(s) produced are directed to, in oneembodiment, one or more polymerization processes for producing variouspolyolefins. (See for example U.S. patent application Ser. No.09/615,376 filed Jul. 13, 2000, which is herein fully incorporated byreference.)

Polymerization processes include solution, gas phase, slurry phase and ahigh pressure processes, or a combination thereof. Particularlypreferred is a gas phase or a slurry phase polymerization of one or moreolefin(s) at least one of which is ethylene or propylene. Polymerizationprocesses include those non-limiting examples described in thefollowing: U.S. Pat. Nos. 4,543,399, 4,588,790, 5,028,670, 5,317,036,5,352,749, 5,405,922, 5,436,304, 5,453,471, 5,462,999, 5,616,661,5,627,242, 5,665,818, 5,677,375, 5,668,228, 5,712,352 and 5,763,543 andEP-A-0 794 200, EP-A-0 802 202, EP-A2- 0 891 990 and EP-B-0 634 421describe gas phase polymerization processes; U.S. Pat. Nos. 3,248,179and 4,613,484, 6,204,344, 6,239,235 and 6,281,300 describe slurry phasepolymerization processes; U.S. Pat. Nos. 4,271,060, 5,001,205, 5,236,998and 5,589,555 describe solution phase polymerization processes; and U.S.Pat. Nos. 3,917,577, 4,175,169, 4,935,397, and 6,127,497 describe highpressure polymerization processes; all of which are herein fullyincorporated by reference.

These polymerization processes utilize a polymerization catalyst thatcan include any one or a combination of the molecular sieve catalystsdiscussed above, however, the preferred polymerization catalysts arethose Ziegler-Natta, Phillips-type, metallocene, metallocene-type andadvanced polymerization catalysts, and mixtures thereof. Non-limitingexamples of polymerization catalysts are described in U.S. Pat. Nos.3,258,455, 3,305,538, 3,364,190, 3,645,992, 4,076,698, 4,115,639,4,077,904 4,482,687, 4,564,605, 4,659,685, 4,721,763, 4,879,359,4,960,741, 4,302,565, 4,302,566, 4,302,565, 4,302,566, 4,124,532,4,302,565, 5,763,723, 4,871,705, 5,120,867, 5,324,800, 5,347,025,5,384,299, 5,391,790, 5,408,017, 5,491,207, 5,455,366, 5,534,473,5,539,124, 5,554,775, 5,621,126, 5,684,098, 5,693,730, 5,698,634,5,710,297, 5,714,427, 5,728,641, 5,728,839, 5,753,577, 5,767,209,5,770,753 and 5,770,664, 5,527,752, 5,747,406, 5,851,945 and 5,852,146,all of which are herein fully incorporated by reference.

In preferred embodiment, the integrated process comprises a polymerizingprocess of one or more olefin(s) in the presence of a polymerizationcatalyst system in a polymerization reactor to produce one or morepolymer products, wherein the one or more olefin(s) having been made byconverting an alcohol, particularly methanol, using a zeolite orzeolite-type molecular sieve catalyst composition. The preferredpolymerization process is a gas phase polymerization process and atleast one of the olefins(s) is either ethylene or propylene, andpreferably the polymerization catalyst system is a supported metallocenecatalyst system. In this embodiment, the supported metallocene catalystsystem comprises a support, a metallocene or metallocene-type compoundand an activator, preferably the activator is a non-coordinating anionor alumoxane, or combination thereof, and most preferably the activatoris alumoxane.

Polymerization conditions vary depending on the polymerization process,polymerization catalyst system and the polyolefin produced. Typicalconditions of polymerization pressure vary from about 100 psig (690kPag) to greater than about 1000 psig (3448 kPag), preferably in therange of from about 200 psig (1379 kPag) to about 500 psig (3448 kPag),and more preferably in the range of from about 250 psig (1724 kPag) toabout 350 psig (2414 kPag). Typical conditions of polymerizationtemperature vary from about 0° C. to about 500° C., preferably fromabout 30° C. to about 350° C., more preferably in the range of fromabout 60° C. to 250° C., and most preferably in the range of from about70° C. to about 150° C. In the preferred polymerization process theamount of polymer being produced per hour is greater than 25,000 lbs/hr(11,300 Kg/hr), preferably greater than 35,000 lbs/hr (15,900 Kg/hr),more preferably greater than 50,000 lbs/hr (22,700 Kg/hr) and mostpreferably greater than 75,000 lbs/hr (29,000 Kg/hr).

The polymers produced by the polymerization processes described aboveinclude linear low density polyethylene, elastomers, plastomers, highdensity polyethylene, low density polyethylene, polypropylene andpolypropylene copolymers. The propylene based polymers produced by thepolymerization processes include atactic polypropylene, isotacticpolypropylene, syndiotactic polypropylene, and propylene random, blockor impact copolymers.

Typical ethylene based polymers have a density in the range of from 0.86g/cc to 0.97 g/cc, a weight average molecular weight to number averagemolecular weight (M_(w)/M_(n)) of greater than 1.5 to about 10 asmeasured by gel permeation chromatography, a melt index (I₂) as measuredby ASTM-D-1238-E in the range from 0.01 dg/min to 1000 dg/min, a meltindex ratio (I₂₁/I₂) (I₂₁ is measured by ASTM-D-1238-F) of from 10 toless than 25, alternatively a I₂₁/I₂ of from greater than 25, morepreferably greater than 40.

Polymers produced by the polymerization process are useful in suchforming operations as film, sheet, and fiber extrusion and co-extrusionas well as blow molding, injection molding and rotary molding; filmsinclude blown or cast films formed by coextrusion or by laminationuseful as shrink film, cling film, stretch film, sealing films, orientedfilms, snack packaging, heavy duty bags, grocery sacks, baked and frozenfood packaging, medical packaging, industrial liners, membranes, etc. infood-contact and non-food contact applications; fibers include meltspinning, solution spinning and melt blown fiber operations for use inwoven or non-woven form to make filters, diaper fabrics, medicalgarments, geotextiles, etc; extruded articles include medical tubing,wire and cable coatings, geomembranes, and pond liners; and moldedarticles include single and multi-layered constructions in the form ofbottles, tanks, large hollow articles, rigid food containers and toys,etc.

In addition to polyolefins, numerous other olefin derived products areformed from the olefin(s) recovered any one of the processes describedabove, particularly the conversion processes, more particularly the GTOprocess or MTO process. These include, but are not limited to,aldehydes, alcohols, acetic acid, linear alpha olefins, vinyl acetate,ethylene dicholoride and vinyl chloride, ethylbenzene, ethylene oxide,cumene, isopropyl alcohol, acrolein, allyl chloride, propylene oxide,acrylic acid, ethylene-propylene rubbers, and acrylonitrile, and trimersand dimers of ethylene, propylene or butylenes.

EXAMPLES

In order to provide a better understanding of the present inventionincluding representative advantages thereof, the following examples areoffered.

Comparative Example 1 Preparation of Molecular Sieve Two Mole TEAOH perMole of P₂O₅

Following a typical SAPO-34 synthesis, the a silicon source, aphosphorous source and an aluminum source and a templating agent weremixed according to the following molar ratio:

2.0TEAOH:1.0Al₂O₃:0.3SiO₂:1.0P₂O₅:50H₂O to form a reaction mixture. Thesources of the ingredients were pseudo-boehmite (an aluminum source),85% phosphoric acid (a phosphorous source), LUDOX HS-40 (a siliconsource), and 40% aqueous solution of TEAOH (an organic templatingagent). The order of mixing was first adding H₃PO₄, then H₂O, followedby Ludox, then Pseudo-boehmite, and finally TEAOH in the molarproportions described above. The reaction mixture was then blended intoa uniform gel using a microhomogenizer. The gel was then placed into aParr bomb with a Teflon liner, and was heated to 180° C. for six days.The solid product formed was centrifuged and washed several times withdeionized water, and was then dried in a 60° C. vacuum oven overnight.The XRD, X-ray powder pattern, of the product confirms that the productis a pure SAPO-34 and having an elemental analysis of the followingmolar composition: Al_(1.0)Si_(0.173)P_(0.834).

Example 2 Preparation of Molecular Sieve Using Polyethylenimine (PEI)Replacing Some TEAOH

Polyethylenimine (available from Aldrich Chemical Company, Inc.,Milwaukee, Wis.) described as(—NHCH₂CH₂—)_(x)[—N(CH₂CH₂NH₂)CH₂CH₂—]_(y)) in a 50 weight percent (wt%) aqueous solution, and having average molecular weight (M_(w)) of750,000, was diluted with water to a 25 wt % solution. The sources ofphosphorous, silicon, aluminum, polymeric base, and templating agentwere added according to the following order: first the phosphoroussource, H₃PO₄, then H₂O, then the silicon source, Ludox, followed by thealuminum source, pseudo-boehmite, then the polymeric base, PEI, andlastly the templating agent, TEAOH. The reaction mixture was blendedusing a microhomogenizer. When higher amount of the polymeric base, PEI,was used, the gel had the consistency of a soft gum coexisting with aclear liquid. The molar ratios of ingredients for three preparationswere as follows:

(1)2.0 PEI monomeric unit(CH₂CH₂NH):1.5TEAOH:1.0Al₂O₃:0.3SiO₂:1.0P₂O₅:50H₂O

(2)4.0 PEI monomeric unit(CH₂CH₂NH):1.0TEAOH:1.0Al₂O₃:0.3SiO₂:1.0P₂O₅:50H₂O

(3)6.0 PEI monomeric unit(CH₂CH₂NH):0.5TEAOH:1.0Al₂O₃:0.3SiO₂:1.0P₂O₅:50H₂O

Each reaction mixture, individually, were sealed in a Teflon lined Parrbomb and were heated to 180° C. for seven days. The solid product formedwere centrifuged and washed several times with deionized water, and thendried in a 60° C. vacuum oven. The X-ray powder diffraction patterns ofthe three molecular sieves synthesized, preparations 1 and 2 producedpure a SAPO-34 phase, while preparation 3 produced a SAPO-34 molecularsieve plus an unidentified phase having two broad peaks at around 15 Åand 7.5 Å d-spacings.

Example 3 Preparation of a Molecular Sieve with One Mole Equivalent ofPolyethylenimine (PEI) Replacing One Mole of TEAOH.

The same procedure as described in Example 1 was used except the moleratio of the sources of silicon, aluminum, and phosphorous, thetemplating agent, and polymeric base, were as follows:

(4)1.0 PEI monomeric unit(CH₂CH₂NH):1.0TEAOH:1.0Al₂O₃:0.3SiO₂:1.0P₂O₅:50H₂O

The reaction mixture was homogenized, sealed in a Teflon lined Parr bomband then heated to 180° C. (hydrothermal reaction temperature) forthirteen days. The solid product formed was centrifuged and washedseveral times with deionized water, and was dried in a 60° C. vacuumoven. The X-ray powder diffraction pattern indicated pure SAPO-34 wasobtained. The SAPO-34 yield was 17.5 wt %, based on the total weight ofthe starting materials. Elemental analysis showed: Al, 16.5%; Si, 2.76%;P, 16.0% corresponding to the composition: Al_(1.0)Si_(0.161)P_(0.845).

Example 4 Preparation of Molecular Sieve Using One Mole Equivalent ofPolyethylenimine (PEI) Replacing One Mole of TEAOH, at 200° C.

The same synthesis procedure as described in Example 3 above was usedexcept that the hydrothermal reaction temperature was set at 200° C.Crystallization proceeded for 5 days. The XRD of the molecular sieveproduct showed a highly crystalline SAPO-34 with a minor amount of anunidentified crystalline impurity. The molecular sieve solid yield was17.0 wt %, based on the total weight of the starting materials. ThisExample 4 illustrates that crystallization time is dramatically reducedby increasing the hydrothermal synthesis reaction temperature.

Example 5 Preparation of Molecular Sieve Using Three Mole Equivalent ofPolyethylenimine (PEI) and One Mole of N,N,N-trimethyladamantylammoniumiodide, at 180° C.

2.07 g H₃PO₄(75%), 3.17 g H₂O, 1.08 g pseudo-boehmite, 0.16 g fumedsilica, 4.03 g polyethylenimine (PEI), and 2.50 gN,N,N-trimethyladamantylammonium iodide was added, in sequence withvigorous blending. The molar ratios of the ingredients are thefollowing:

(5) 3.0(CH₂CH₂NH):1.0R⁺I⁻:1.0Al₂O₃:0.3SiO₂:1.0P₂O₅:50H₂O, where R⁺I⁻ isN,N,N-trimethyladamantylammonium iodide.

In one embodiment, a molecular sieve, most preferably a SAPO molecularsieve, even more particularly a SAPO-34 molecular sieve, is formed usingthe templating agent, N,N,N-trimethyladamantylammonium iodide. Themixture was sealed, and crystallization carried out, as described abovein Example 4. After 4 days of crystallization the crystalline molecularsieve was isolated by centrifugation and was washed with deionizedwater. The XRD of the solid product indicated that pure SAPO-34 (CHAstructure-type) was obtained. The molecular sieve solid yield was 19.3wt % based on the total weight of the starting materials. This exampleillustrates the use of a quaternary ammonium iodide salt as thetemplating agent, instead of the more expensive quaternary ammoniumhydroxide, when a polymeric base is used to control the pH.

While the present invention has been described and illustrated byreference to particular embodiments, those of ordinary skill in the artwill appreciate that the invention lends itself to variations notnecessarily illustrated herein. For example, it is contemplated that themolecular sieve catalyst composition is useful in the inter-conversionof olefin(s), oxygenate to gasoline conversions reactions, malaeicanhydride, phthalic anyhdride and acrylonitrile formulation, vapor phasemethanol synthesis, and various Fischer Tropsch reactions. It is furthercontemplated that a plug flow, fixed bed or fluidized bed process areused in combination, particularly in different reaction zones within asingle or multiple reactor system. It is also contemplated the molecularsieves described herein are useful as absorbents, adsorbents, gasseparators, detergents, water purifiers, and other various uses such asagriculture and horticulture. For this reason, then, reference should bemade solely to the appended claims for purposes of determining the truescope of the present invention.

We claim:
 1. A method for synthesizing a molecular sieve, the methodcomprising the steps of: (a) forming a reaction mixture comprising: atleast one templating agent and at least two of the group consisting of asilicon source, a phosphorus source and an aluminum source; (b)introducing to the reaction mixture a non-ionic polymeric base; and (c)recovering the molecular sieve from the reaction mixture.
 2. The methodclaim 1 wherein the polymeric base is a soluble polymeric base.
 3. Themethod of claim 1 wherein the polymeric base is a polymeric imine. 4.The method of claim 1 wherein the polymeric base is represented by theformula: (—NHCH₂CH₂—)_(m)[—N(CH₂CH₂NH₂)CH₂CH₂—]_(n), wherein m is from10 to 20,000, and n is from 1 to 2,000.
 5. The method claim 1 whereinthe mole ratio of the monomeric unit of the polymeric base to thetemplating agent is less than
 20. 6. The method of claim 1 wherein thereaction mixture is maintained at a pH in the range of from 3 to
 10. 7.The method of claim 1 wherein the templating agent is a quaternaryammonium hydroxide or a quaternary ammonium salt.
 8. The method of claim1 wherein the polymeric base is selected from the group consisting of:epichlorohydrin modified polyethylenimine, ethoxylated polyethylenimine,polypropylenimine diamine dendrimers, poly(allylamine),poly(1,2-dihydro-2,2,4-trimethylquinoline), andpoly(dimethylamine-co-epichlorohydrin-co-ethylenediamine).
 9. The methodof claim 1 wherein the reaction mixture comprises: at least onetemplating agent and a silicon source, a phosphorus source and analuminum source.
 10. The method of claim 1 wherein the reaction mixturecomprises: at least one templating agent and a phosphorus source and analuminum source.
 11. A method for synthesizing a molecular sieve, themethod comprising the steps of: (a) combining at least one templatingagent and at least two of the group consisting of a silicon source, aphosphorus source and an aluminum source; and (b) adding a non-ionicpolymeric base.
 12. The method of claim 11, wherein the method furthercomprises the step of: (c) crystallizing the molecular sieve at atemperature less than 200° C.
 13. The method of claim 11 wherein thenon-ionic polymeric base is soluble.
 14. The method of claim 11 whereinthe non-ionic polymeric base is represented by the formula:(—NHCH₂CH₂—)_(m)[—N(CH₂CH₂NH₂)CH₂CH₂—]_(n), wherein m is from 10 to20,000, and n is from 1 to 2,000.
 15. The method claim 11 wherein themole ratio of the monomeric unit of the non-ionic polymeric base to thetemplating agent is less than
 20. 16. The method of claim 15 wherein thenon-ionic polymeric base in an aqueous solution has a pH in the range offrom 8 to
 14. 17. The method of claim 11 wherein the templating agent isa quaternary ammonium hydroxide or a quaternary ammonium salt.
 18. Themethod of claim 11 wherein the at least one templating agent is combinedwith a silicon source, a phosphorus source and an aluminum source. 19.The method of claim 11 wherein the non-ionic polymeric base is apolymeric imine.
 20. A method for forming a molecular sieve catalystcomposition from the molecular sieve recovered in step (c) of claim 1,wherein the method further comprises the step of: contacting themolecular sieve with a matrix material, optionally with a binder. 21.The method of claim 20 wherein the molecular sieve recovered is a SAPOmolecular sieve.
 22. The method of claim 20 wherein the molecular sieverecovered is an ALPO molecular sieve.
 23. The method of claim 20 whereinthe molecular sieve catalyst composition is spray dried.
 24. The methodof claim 1, wherein the polymeric base is represented by the formula:(—NHCH₂CH₂—)_(m)[—N(CH₂CH₂NH₂)CH₂CH₂—]_(n), wherein m is from 10 to20,000, and n is from 0 to 2,000.
 25. The method of claim 11, whereinthe polymeric base is represented by the formula:(—NHCH₂CH₂—)_(m)[—N(CH₂CH₂NH₂)CH₂CH₂—]_(n), wherein m is from 10 to20,000, and n is from 0 to 2,000.
 26. A method for synthesizing amolecular sieve, the method comprising the steps of; (a) providing areaction mixture comprising at least one templating agent and at leasttwo of the group consisting of a silicon source, a phosphorus source andan aluminum source; and (b) contacting the reaction mixture with apolymeric base selected from the group consisting of polyethylenimine,epichlorohydrin modified polyethylenimine, ethoxylated polyethylenimine,polypropylenimine diamine dendrimers, poly(allylamine),poly(1,2-dihydro-2,2,4-trimethylquinoline),poly(dimethylamine-co-epichlorohydrin-co-ethylenediamine) and mixturesthereof, to form the molecular sieve.
 27. The method of claim 26,further comprising (c) recovering the molecular sieve from the reactionmixture.
 28. The method of claim 26, wherein the reaction mixturecomprises at least one templating agent, a silicon source, a phosphorussource, and an aluminum source.
 29. A method for forming a molecularsieve catalyst composition, the method comprising the steps of: (a)providing a reaction mixture comprising at least one templating agentand at least two of the group consisting of a silicon source, aphosphorus source and an aluminum source; (b) contacting the reactionmixture with a polymeric base selected from the group consisting ofpolyethylenimine, epichlorohydrin modified polyethylenimine, ethoxylatedpolyethylenimine, polypropylenimine diamine dendrimers,poly(allylamine), poly(1,2-dihydro-2,2,4-trimethylquinoline),poly(dimethylamine-co-epichlorohydrin-co-ethylenediamine) and mixturesthereof, to form a molecular sieve; (c) recovering the molecular sievefrom the reaction mixture; and (d) contacting the molecular sieve with amatrix material to form a molecular sieve catalyst composition.
 30. Themethod of claim 29, wherein the reaction mixture comprises at least onetemplating agent, a silicon source, a phosphorus source, and an aluminumsource.
 31. A method for synthesizing a molecular sieve, the methodcomprising the steps of: (a) providing a reaction mixture comprising atleast one templating agent and at least two of the group consisting of asilicon source, a phosphorus source and an aluminum source; and (b)contacting the reaction mixture with a polymeric base of formula:(—NHCH₂CH₂—)_(m)[—N(CH₂CH₂NH₂)CH₂CH₂—]_(n), wherein m is from 10 to20,000, and n is from 0 to 2,000, to form the molecular sieve.
 32. Themethod of claim 31, further comprising (c) recovering the molecularsieve from the reaction mixture.
 33. The method of claim 31, wherein thereaction mixture comprises at least one templating agent, a siliconsource, a phosphorus source, and an aluminum source.
 34. The method ofclaim 31, wherein n is from 1 to
 2000. 35. A method for forming amolecular sieve catalyst composition, the method comprising the stepsof: (a) providing a reaction mixture comprising at least one templatingagent and at least two of the group consisting of a silicon source, aphosphorus source and an aluminum source; (b) contacting the reactionmixture with a polymeric base of formula(—NHCH₂CH₂—)_(m)[—N(CH₂CH₂NH₂)CH₂CH₂—]_(n), wherein m is from 10 to20,000, and n is from 0 to 2,000, to form a molecular sieve; (c)recovering the molecular sieve from the reaction mixture; and (d)contacting the molecular sieve with a matrix material to form amolecular sieve catalyst composition.
 36. The method of claim 35,wherein the reaction mixture comprises at least one templating agent, asilicon source, a phosphorus source, and an aluminum source.
 37. Themethod of claim 35, wherein n is from 1 to 2000.